Kosti Tapio

Custom-shaped metal nanostructures based on DNA origami silhouettes

The DNA origami technique provides an intriguing possibility to develop customized nanostructures for various bionanotechnological purposes. One target is to create tailored bottom-up-based plasmonic devices and metamaterials based on DNA metallization or controlled attachment of nanoparticles to the DNA designs. In this article, we demonstrate an alternative approach: DNA origami nanoshapes can be utilized in creating accurate, uniform and entirely metallic (e.g. gold, silver and copper) nanostructures on silicon substrates. The technique is based on developing silhouettes of the origamis in the grown silicon dioxide layer, and subsequently using this layer as a mask for further patterning. The proposed method has a high spatial resolution, and the fabrication yields can approach 90%. The approach allows a cost-effective, parallel, large-scale patterning on a chip with fully tailored metallic nanostructures; the DNA origami shape and the applied metal can be specifically chosen for each conceivable implementation.

DNA-based enzyme reactors and systems

During recent years, the possibility to create custom biocompatible nanoshapes using DNA as a building material has rapidly emerged. Further, these rationally designed DNA structures could be exploited in positioning pivotal molecules, such as enzymes, with nanometer-level precision. This feature could be used in the fabrication of artificial biochemical machinery that is able to mimic the complex reactions found in living cells. Currently, DNA-enzyme hybrids can be used to control (multi-enzyme) cascade reactions and to regulate the enzyme functions and the reaction pathways. Moreover, sophisticated DNA structures can be utilized in encapsulating active enzymes and delivering the molecular cargo into cells. In this review, we focus on the latest enzyme systems based on novel DNA nanostructures: enzyme reactors, regulatory devices and carriers that can find uses in various biotechnological and nanomedical applications.

One-step large-scale deposition of salt-free DNA origami nanostructures

DNA origami nanostructures have tremendous potential to serve as versatile platforms in self-assembly -based nanofabrication and in highly parallel nanoscale patterning. However, uniform deposition and reliable anchoring of DNA nanostructures often requires specific conditions, such as pre-treatment of the chosen substrate or a fine-tuned salt concentration for the deposition buffer. In addition, currently available deposition techniques are suitable merely for small scales. In this article, we exploit a spray-coating technique in order to resolve the aforementioned issues in the deposition of different 2D and 3D DNA origami nanostructures. We show that purified DNA origamis can be controllably deposited on silicon and glass substrates by the proposed method. The results are verified using either atomic force microscopy or fluorescence microscopy depending on the shape of the DNA origami. DNA origamis are successfully deposited onto untreated substrates with surface coverage of about 4 objects/mm2. Further, the DNA nanostructures maintain their shape even if the salt residues are removed from the DNA origami fabrication buffer after the folding procedure. We believe that the presented one-step spray-coating method will find use in various fields of material sciences, especially in the development of DNA biochips and in the fabrication of metamaterials and plasmonic devices through DNA metallisation.

Influence of Nitrogen Doping on Device Operation for TiO2-Based Solid-State Dye-Sensitized Solar Cells: Photo-Physics from Materials to Devices

Solid-state dye-sensitized solar cells (ssDSSC) constitute a major approach to photovoltaic energy conversion with efficiencies over 8% reported thanks to the rational design of efficient porous metal oxide electrodes, organic chromophores, and hole transporters. Among the various strategies used to push the performance ahead, doping of the nanocrystalline titanium dioxide (TiO2) electrode is regularly proposed to extend the photo-activity of the materials into the visible range. However, although various beneficial effects for device performance have been observed in the literature, they remain strongly dependent on the method used for the production of the metal oxide, and the influence of nitrogen atoms on charge kinetics remains unclear. To shed light on this open question, we synthesized a set of N-doped TiO2 nanopowders with various nitrogen contents, and exploited them for the fabrication of ssDSSC. Particularly, we carefully analyzed the localization of the dopants using X-ray photo-electron spectroscopy (XPS) and monitored their influence on the photo-induced charge kinetics probed both at the material and device levels. We demonstrate a strong correlation between the kinetics of photo-induced charge carriers probed both at the level of the nanopowders and at the level of working solar cells, illustrating a direct transposition of the photo-physic properties from materials to devices.

Metallic Nanostructures Based on DNA Nanoshapes

Metallic nanostructures have inspired extensive research over several decades, particularly within the field of nanoelectronics and increasingly in plasmonics. Due to the limitations of conventional lithography methods, the development of bottom-up fabricated metallic nanostructures has become more and more in demand. The remarkable development of DNA-based nanostructures has provided many successful methods and realizations for these needs, such as chemical DNA metallization via seeding or ionization, as well as DNA-guided lithography and casting of metallic nanoparticles by DNA molds. These methods offer high resolution, versatility and throughput and could enable the fabrication of arbitrarily-shaped structures with a 10-nm feature size, thus bringing novel applications into view. In this review, we cover the evolution of DNA-based metallic nanostructures, starting from the metallized double-stranded DNA for electronics and progress to sophisticated plasmonic structures based on DNA origami objects.

Plasmonic nanostructures through DNA-assisted lithography

DALI combines DNA origami with conventional top-down fabrication for creating designer high-resolution plasmonic nanostructures. Programmable self-assembly of nucleic acids enables the fabrication of custom, precise objects with nanoscale dimensions. These structures can be further harnessed as templates to build novel materials such as metallic nanostructures, which are widely used and explored because of their unique optical properties and their potency to serve as components of novel metamaterials. However, approaches to transfer the spatial information of DNA constructions to metal nanostructures remain a challenge. We report a DNA-assisted lithography (DALI) method that combines the structural versatility of DNA origami with conventional lithography techniques to create discrete, well-defined, and entirely metallic nanostructures with designed plasmonic properties. DALI is a parallel, high-throughput fabrication method compatible with transparent substrates, thus providing an additional advantage for optical measurements, and yields structures with a feature size of ~10 nm. We demonstrate its feasibility by producing metal nanostructures with a chiral plasmonic response and bowtie-shaped nanoantennas for surface-enhanced Raman spectroscopy. We envisage that DALI can be generalized to large substrates, which would subsequently enable scale-up production of diverse metallic nanostructures with tailored plasmonic features.

Improved antifouling properties and selective biofunctionalization of stainless steel by employing heterobifunctional silane-polyethylene glycol overlayers and avidin-biotin technology

A straightforward solution-based method to modify the biofunctionality of stainless steel (SS) using heterobifunctional silane-polyethylene glycol (silane-PEG) overlayers is reported. Reduced nonspecific biofouling of both proteins and bacteria onto SS and further selective biofunctionalization of the modified surface were achieved. According to photoelectron spectroscopy analyses, the silane-PEGs formed less than 10 Å thick overlayers with close to 90% surface coverage and reproducible chemical compositions. Consequently, the surfaces also became more hydrophilic, and the observed non-specific biofouling of proteins was reduced by approximately 70%. In addition, the attachment of E. coli was reduced by more than 65%. Moreover, the potential of the overlayer to be further modified was demonstrated by successfully coupling biotinylated alkaline phosphatase (bAP) to a silane-PEG-biotin overlayer via avidin-biotin bridges. The activity of the immobilized enzyme was shown to be well preserved without compromising the achieved antifouling properties. Overall, the simple solution-based approach enables the tailoring of SS to enhance its activity for biomedical and biotechnological applications.

Aluminum Plasmonics: Fabrication and Characterization of Broadly Tunable Plasmonic Surfaces for Plasmon Molecule Strong-Coupling and Fluorescence Enhancement

Our work based on previous studies [1, 2] confirms, that simple aluminum nanostructures can be utilized as effective plasmonic resonators over a broad range of frequencies and wavelengths. The nanostructured surfaces, fabricated by electron-beam lithography demonstrated relatively narrow-band resonances and are suitable for various plasmonic applications ranging from metal enhanced fluorescence to strong-coupling [1, 2, 3, 4, 5] experiments. We represent data for molecule-plasmon coupling near the strong coupling limit and demonstrate that these aluminum structures do act as fluorescence increasing substrates. In this work, we used two different types of dyes. We studied the narrow band j-aggregate forming TDBC with almost no Stokes-shift and a recently developed large Stokes-shift dye commercially available under the name ATTO 490LS. Anti-crossing behavior was observed for both dyes, but a clear Rabi split for the ATTO 490LS was not fully reached. We observed a Rabi split of more than 160 meV for the TDBC sample (Fig. 1) and enhanced selectively the fluorescence of the ATTO 490LS dye more than 3.5 times.