Bramaramba Gnapareddy

Construction and characterization of Cu2+, Ni2+, Zn2+, and Co2+ modified-DNA crystals

We studied the physical characteristics of modified-DNA (M-DNA) double crossover crystals fabricated via substrate-assisted growth with various concentrations of four different divalent metallic ions, Cu(2+), Ni(2+), Zn(2+), and Co(2+). Atomic force microscopy (AFM) was used to test the stability of the M-DNA crystals with different metal ion concentrations. The AFM images show that M-DNA crystals formed without deformation at up to the critical concentrations of 6 mM of [Cu(2+)], 1.5 mM of [Ni(2+)], 1 mM of [Zn(2+)], and 1 mM of [Co(2+)]. Above these critical concentrations, the M-DNA crystals exhibited deformed, amorphous structures. Raman spectroscopy was then used to identify the preference of the metal ion coordinate sites. The intensities of the Raman bands gradually decreased as the concentration of the metal ions increased, and when the metal ion concentrations increased beyond the critical values, the Raman band of the amorphous M-DNA was significantly suppressed. The metal ions had a preferential binding order in the DNA molecules with G-C and A-T base pairs followed by the phosphate backbone. A two-probe station was used to measure the electrical current-voltage properties of the crystals which indicated that the maximum currents of the M-DNA complexes could be achieved at around the critical concentration of each ion. We expect that the functionalized ion-doped M-DNA crystals will allow for efficient devices and sensors to be fabricated in the near future.

Energy Band Gap and Optical Transition of Metal Ion Modified Double Crossover DNA Lattices

We report on the energy band gap and optical transition of a series of divalent metal ion (Cu(2+), Ni(2+), Zn(2+), and Co(2+)) modified DNA (M-DNA) double crossover (DX) lattices fabricated on fused silica by the substrate-assisted growth (SAG) method. We demonstrate how the degree of coverage of the DX lattices is influenced by the DX monomer concentration and also analyze the band gaps of the M-DNA lattices. The energy band gap of the M-DNA, between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO), ranges from 4.67 to 4.98 eV as judged by optical transitions. Relative to the band gap of a pristine DNA molecule (4.69 eV), the band gap of the M-DNA lattices increases with metal ion doping up to a critical concentration and then decreases with further doping. Interestingly, except for the case of Ni(2+), the onset of the second absorption band shifts to a lower energy until a critical concentration and then shifts to a higher energy with further increasing the metal ion concentration, which is consistent with the evolution of electrical transport characteristics. Our results show that controllable metal ion doping is an effective method to tune the band gap energy of DNA-based nanostructures.

A 2D DNA lattice as an ultrasensitive detector for beta radiations.

There is growing demand for the development of efficient ultrasensitive radiation detectors to monitor the doses administered to individuals during therapeutic nuclear medicine which is often based on radiopharmaceuticals, especially those involving beta emitters. Recently biological materials are used in sensors in the nanobio disciplines due to their abilities to detect specific target materials or sites. Artificially designed two-dimensional (2D) DNA lattices grown on a substrate were analyzed after exposure to pure beta emitters, (90)Sr-(90)Y. We studied the Raman spectra and reflected intensities of DNA lattices at various distances from the source with different exposure times. Although beta particles have very low linear energy transfer values, the significant physical and chemical changes observed throughout the extremely thin, ∼0.6 nm, DNA lattices suggested the feasibility of using them to develop ultrasensitive detectors of beta radiations.

Chemical and Physical Characteristics of Doxorubicin Hydrochloride Drug-Doped Salmon DNA Thin Films

Double-stranded salmon DNA (SDNA) was doped with doxorubicin hydrochloride drug molecules (DOX) to determine the binding between DOX and SDNA, and DOX optimum doping concentration in SDNA. SDNA thin films were prepared with various concentrations of DOX by drop-casting on oxygen plasma treated glass and quartz substrates. Fourier transform infrared (FTIR) spectroscopy was employed to investigate the binding sites for DOX in SDNA, and electrical and photoluminescence (PL) analyses were used to determine the optimum doping concentration of DOX. The FTIR spectra showed that up to a concentration of 30 μM of DOX, there was a tendency for binding with a periodic orientation via intercalation between nucleosides. The current and PL intensity increased as the DOX concentration increased up to 30 μM, and then as the concentration of DOX further increased, we observed a decrease in current as well as PL quenching. Finally, the optical band gap and second band onset of the transmittance spectra were analyzed to further verify the DOX binding and optimum doping concentration into SDNA thin films as a function of the DOX concentration.

Ultra-low Doping on Two-Dimensional Transition Metal Dichalcogenides using DNA Nanostructure Doped by a Combination of Lanthanide and Metal Ions.

Here, we propose a novel DNA-based doping method on MoS2 and WSe2 films, which enables ultra-low n- and p-doping control and allows for proper adjustments in device performance. This is achieved by selecting and/or combining different types of divalent metal and trivalent lanthanide (Ln) ions on DNA nanostructures, using the newly proposed concept of Co-DNA (DNA functionalized by both divalent metal and trivalent Ln ions). The available n-doping range on the MoS2 by Ln-DNA is between 6 × 109 and 2.6 × 1010 cm−2. The p-doping change on WSe2 by Ln-DNA is adjusted between −1.0 × 1010 and −2.4 × 1010 cm−2. In Eu3+ or Gd3+-Co-DNA doping, a light p-doping is observed on MoS2 and WSe2 (~1010 cm−2). However, in the devices doped by Tb3+ or Er3+-Co-DNA, a light n-doping (~1010 cm−2) occurs. A significant increase in on-current is also observed on the MoS2 and WSe2 devices, which are, respectively, doped by Tb3+- and Gd3+-Co-DNA, due to the reduction of effective barrier heights by the doping. In terms of optoelectronic device performance, the Tb3+ or Er3+-Co-DNA (n-doping) and the Eu3+ or Gd3+-Co-DNA (p-doping) improve the MoS2 and WSe2 photodetectors, respectively. We also show an excellent absorbing property by Tb3+ ions on the TMD photodetectors.

Tunable near white light photoluminescence of lanthanide ion (Dy3+, Eu3+ and Tb3+) doped DNA lattices

For more than two decades, structural DNA nanotechnology has been investigated, yet researchers still have not clearly determined the functional changes and the applicability of DNA structures resulting from the introduction of a variety of ions. Lanthanide ions, such as Dy3+, Eu3+ and Tb3+, are interesting rare earth ions that have unique characteristics applicable to photonics. Here, we have constructed lanthanide ion doped double-crossover DNA lattices, a new class of functional DNA lattices, grown on a silica substrate. Deformation-free lattices were fabricated on a given substrate, and dopant ions were introduced to study their photoluminescence characteristics. The photoluminescence of the lanthanide ion-doped DNA lattices exhibited broad emission spectra in the visible region and a tendency of near white light emission composed of various colours. The intensity of the distinct spectral lines produced by the photoluminescence increased as the doping concentration of the ions reached the critical point, and the intensity then decreased with a further increase in the ions. Photoluminescence quenching was also observed when the excitation wavelength increased. These phenomena are the result of energy transfer between the DNA and the dopant ions. Finally, we make use of chromaticity diagrams to identify the colour coordinates of the luminescence produced by the lanthanide ion-doped DNA lattices, and this information may be useful to construct efficient bio-photonic devices or sensors in the future.

M-DNA/Transition Metal Dichalcogenide Hybrid Structure-based Bio-FET sensor with Ultra-high Sensitivity

Here, we report a high performance biosensor based on (i) a Cu2+-DNA/MoS2 hybrid structure and (ii) a field effect transistor, which we refer to as a bio-FET, presenting a high sensitivity of 1.7 × 103 A/A. This high sensitivity was achieved by using a DNA nanostructure with copper ions (Cu2+) that induced a positive polarity in the DNA (receptor). This strategy improved the detecting ability for doxorubicin-like molecules (target) that have a negative polarity. Very short distance between the biomolecules and the sensor surface was obtained without using a dielectric layer, contributing to the high sensitivity. We first investigated the effect of doxorubicin on DNA/MoS2 and Cu2+-DNA/MoS2 nanostructures using Raman spectroscopy and Kelvin force probe microscopy. Then, we analyzed the sensing mechanism and performance in DNA/MoS2- and Cu2+-DNA/MoS2-based bio-FETs by electrical measurements (ID-VG at various VD) for various concentrations of doxorubicin. Finally, successful operation of the Cu2+-DNA/MoS2 bio-FET was demonstrated for six cycles (each cycle consisted of four steps: 2 preparation steps, a sensing step, and an erasing step) with different doxorubicin concentrations. The bio-FET showed excellent reusability, which has not been achieved previously in 2D biosensors.

Morphological and Optoelectronic Characteristics of Double and Triple Lanthanide Ion-Doped DNA Thin Films

Double and triple lanthanide ion (Ln(3+))-doped synthetic double crossover (DX) DNA lattices and natural salmon DNA (SDNA) thin films are fabricated by the substrate assisted growth and drop-casting methods on given substrates. We employed three combinations of double Ln(3+)-dopant pairs (Tb(3+)-Tm(3+), Tb(3+)-Eu(3+), and Tm(3+)-Eu(3+)) and a triple Ln(3+)-dopant pair (Tb(3+)-Tm(3+)-Eu(3+)) with different types of Ln(3+), (i.e., Tb(3+) chosen for green emission, Tm(3+) for blue, and Eu(3+) for red), as well as various concentrations of Ln(3+) for enhancement of specific functionalities. We estimate the optimum concentration of Ln(3+) ([Ln(3+)]O) wherein the phase transition of Ln(3+)-doped DX DNA lattices occurs from crystalline to amorphous. The phase change of DX DNA lattices at [Ln(3+)]O and a phase diagram controlled by combinations of [Ln(3+)] were verified by atomic force microscope measurement. We also developed a theoretical method to obtain a phase diagram by identifying a simple relationship between [Ln(3+)] and [Ln(3+)]O that in practice was found to be in agreement with experimental results. Finally, we address significance of physical characteristics-current for evaluating [Ln(3+)]O, absorption for understanding the modes of Ln(3+) binding, and photoluminescence for studying energy transfer mechanisms-of double and triple Ln(3+)-doped SDNA thin films. Current and photoluminescence in the visible region increased as the varying [Ln(3+)] increased up to a certain [Ln(3+)]O, then decreased with further increases in [Ln(3+)]. In contrast, the absorbance peak intensity at 260 nm showed the opposite trend, as compared with current and photoluminescence behaviors as a function of varying [Ln(3+)]. A DNA thin film with varying combinations of [Ln(3+)] might provide immense potential for the development of efficient devices or sensors with increasingly complex functionality.

Coverage percentage and raman measurement of cross-tile and scaffold cross-tile based DNA nanostructures.

We present two free-solution annealed DNA nanostructures consisting of either cross-tile CT1 or CT2. The proposed nanostructures exhibit two distinct structural morphologies, with one-dimensional (1D) nanotubes for CT1 and 2D nanolattices for CT2. When we perform mica-assisted growth annealing with CT1, a dramatic dimensional change occurs where the 1D nanotubes transform into 2D nanolattices due to the presence of the substrate. We assessed the coverage percentage of the 2D nanolattices grown on the mica substrate with CT1 and CT2 as a function of the concentration of the DNA monomer. Furthermore, we fabricated a scaffold cross-tile (SCT), which is a new design of a modified cross-tile that consists of four four-arm junctions with a square aspect ratio. For SCT, eight oligonucleotides are designed in such a way that adjacent strands with sticky ends can produce continuous arms in both the horizontal and vertical directions. The SCT was fabricated via free-solution annealing, and self-assembled SCT produces 2D nanolattices with periodic square cavities. All structures were observed via atomic force microscopy. Finally, we fabricated divalent nickel ion (Ni(2+))- and trivalent dysprosium ion (Dy(3+))-modified 2D nanolattices constructed with CT2 on a quartz substrate, and the ion coordinations were examined via Raman spectroscopy.

Nature-Inspired Construction of Two-Dimensionally Self-Assembled Peptide on Pristine Graphene

Peptide assemblies have received significant attention because of their important role in biology and applications in bionanotechnology. Despite recent efforts to elucidate the principles of peptide self-assembly for developing novel functional devices, peptide self-assembly on two-dimensional nanomaterials has remained challenging. Here, we report nature-inspired two-dimensional peptide self-assembly on pristine graphene via optimization of peptide-peptide and peptide-graphene interactions. Two-dimensional peptide self-assembly was designed based on statistical analyses of >104 protein structures existing in nature and atomistic simulation-based structure predictions. We characterized the structures and surface properties of the self-assembled peptide formed on pristine graphene. Our study provides insights into the formation of peptide assemblies coupled with two-dimensional nanomaterials for further development of nanobiocomposite devices.