DNA foams constructed by freeze drying and their optoelectronic characteristics.

The distinctive properties of DNA make it a promising biomaterial to use in nanoscience and nanotechnology. In the present study, DNA foam was fabricated into multi-dimensional shapes using a freeze drying process with liquid nitrogen and 3D printed molds. The physicochemical and optoelectronic properties of the fabricated DNA foams were investigated using Fourier transform infrared (FTIR) spectrum, X-ray photoelectron spectrum (XPS), thermogravimetric analysis (TGA), ultraviolet-visible (UV-Vis) absorption spectrum, and current-voltage (I-V) characteristics to understand the changes formed in the DNA structure and their effect on properties during the fabrication of DNA foam. The FTIR and XPS analyses confirmed that nitrogen was diffusing into the DNA structure during the DNA foam fabrication. The diffused nitrogen caused a decrease in bond lengths, strong chemical bonds, compaction of DNA structure, existence of additional carbon-nitrogen bonds, and variation in the electron density of the base elements in DNA. These changes in the DNA structure of the DNA foam were reflected in their chemical, optical, and electrical properties. Furthermore, the proper utilization of DNA foams as a template for functional materials by embedding carbon nanotubes (CNTs) and thermocolor was demonstrated.

Nanomaterial-Embedded DNA Films on 2D Frames.

Recently, 3D printing has provided opportunities for designing complex structures with ease. These printed structures can serve as molds for complex materials such as DNA and cetyltrimethylammonium chloride (CTMA)-modified DNA that have easily tunable functionalities via the embedding of various nanomaterials such as ions, nanoparticles, fluorophores, and proteins. Herein, we develop a simple and efficient method for constructing DNA flat and curved films containing water-soluble/thermochromatic dyes and di/trivalent ions and CTMA-modified DNA films embedded with organic light-emitting molecules (OLEM) with the aid of 2D/3D frames made by a 3D printer. We study the Raman spectra, current, and resistance of Cu2+-doped and Tb3+-doped DNA films and the photoluminescence of OLEM-embedded CTMA-modified DNA films to better understand the optoelectric characteristics of the samples. Compared to pristine DNA, ion-doped DNA films show noticeable variation of Raman peak intensities, which might be due to the interaction between the ion and phosphate backbone of DNA and the intercalation of ions in DNA base pairs. As expected, ion-doped DNA films show an increase of current with an increase in bias voltage. Because of the presence of metallic ions, DNA films with embedded ions showed relatively larger current than pristine DNA. The photoluminescent emission peaks of CTMA-modified DNA films with OLEMRed, OLEMGreen, and OLEMBlue were obtained at the wavelengths of 610, 515, and 469 nm, respectively. Finally, CIE color coordinates produced from CTMA-modified DNA films with different OLEM color types were plotted in color space. It may be feasible to produce multilayered DNA films as well. If so, multilayered DNA films embedded with different color dyes, ions, fluorescent materials, nanoparticles, proteins, and drug molecules could be used to realize multifunctional physical devices such as energy harvesting and chemo-bio sensors in the near future.

Catalytic Enhancement of CO Oxidation on LaFeO3 Regulated by Ruddlesden-Popper Stacking Faults.

The influence of planar defects, in the form of stacking faults, within perovskite oxides on catalytic activity has received little attention because controlling stacking-fault densities presents a major synthetic challenge. Furthermore, stacking faults in ceramics are not thought to appreciably impact surface chemistry, which partly explains why their direct effect on catalysis is generally ignored. Here, we show that Ruddlesden-Popper (RP) stacking faults in otherwise stoichiometric LaFeO3 can be broadly controlled by modulating the ceramic synthesis route. Electronic structure calculations along with electron microscopy and spectroscopy show that energetically favorable RP faults occur both near the surface and in bunches and enhance CO oxidation kinetics. Density functional theory (DFT) + U shows that subsurface RP faults strengthen the adsorption and co-adsorption of CO, O, and O2, which could lower the apparent activation energy of CO oxidation on faulted catalysts compared to that on their pristine counterparts. Our work suggests that planar defects should be considered a new and useful feature in hierarchal nanoscale design of future catalysts.

NIR absorbing Au nanoparticle decorated layered double hydroxide nanohybrids for photothermal therapy and fluorescence imaging of cancer cells.

Among inorganic nanomaterials, layered double hydroxides (LDHs) and gold nanoparticles (Au NPs) have received great attention in nanobiomedicine due to their unique properties. In this work, we have designed a nanohybrid of an LDH with Au NPs (LDH-Au) in order to use it for photothermal therapy, and optical and fluorescence imaging of cancer cells. The structural characteristics of the nanohybrid are investigated using X-ray diffraction, infrared spectroscopy, electron microscopy and elemental analyses. The extinction spectra of the nanohybrid exhibits broad absorption ranging from the visible to near infrared (NIR) region (500-1000 nm). The photothermal activity of the nanohybrid is explored using NIR laser irradiation. The electric field enhancement in the nanohybrid due to the interaction of Au NPs on the LDH is speculated through finite-difference time-domain (FDTD) calculations. The LDH-Au nanohybrid is found to be biocompatible with normal murine fibroblast (L929), human breast cancer (MCF-7) and cervical cancer (HeLa) cell lines up to a concentration of 1 mg mL-1. The nanohybrid is explored for in vitro photothermal therapy of MCF-7 and HeLa cell lines. As a photothermal agent, the nanohybrid shows that 10 min exposure to an 808 nm laser (500 mW) is adequate to inhibit about 70% of cancer cells. Further, the nanohybrid is tagged with FITC to study both optical and fluorescence imaging with MCF-7 cell lines. The results demonstrate that the LDH-Au nanohybrid provides an innovative approach to photothermal therapy, and optical and fluorescence imaging of cancer cells.