Petia Atanasova

Virus-templated synthesis of ZnO nanostructures and formation of field-effect transistors.

The search for novel methods for the synthesis of nanostructured materials is an important step towards the miniaturization of multifunctional devices, which requires careful and appropriate integration of various materials into a single unit. However, most of the conventional synthesis methods for multicomponent systems involve harsh reaction conditions and thereby introduce limitations in the choice of materials to be combined. For instance, in ceramic synthesis methods, extreme heating and/or pressure are often used, which may be inapplicable to certain components of a device structure. Further factors critical to the miniaturization are the size of the obtained powder particles and their tendency to agglomerate. Hence, the integration of different materials is still a challenging goal and can hardly be achieved by conventional processing. Biomineralization is a process used by organisms to generate composite materials composed of organic and inorganic phases, which often exhibit exceptional properties. [ 1 ] Organic molecules, such as peptides, proteins, or polysaccharides, guide the crystal growth at ambient conditions that eventually determine the morphology and the functional properties of the materials. [ 2 ] The integration of biomolecules as templates or structure-directing agents, on the other hand, offers the opportunity to explore alternative low-temperature methods in the synthesis of bioinorganic hybrid materials with novel tailored functionalities. [ 3 , 4 ] For some applications, however, the adaptation of bionic mineralization approaches to the synthesis of artifi cial composite materials is not possible, since no interactions between the inorganic phase

DNA-templated synthesis of ZnO thin layers and nanowires

In this paper, we report a novel synthetic approach towards electrically conductive ZnO nanowires close to ambient conditions using lambda-DNA as a template. Initially, the suitability of DNA to assemble ZnO nanocrystals into thin coatings was investigated. The ZnO nanowires formed on stretched and aligned lambda-DNA molecules were prepared via chemical bath deposition (CBD) of zinc acetate in methanol solution in the presence of polyvinylpyrrolidone (PVP). After 10 deposition cycles, the nanowires exceed 10 microm in length and the height can be varied from 12 to around 40 nm. The nanocrystalline structure of the ZnO wires was confirmed by high-resolution transmission electron microscopy (HRTEM). The electrical conductivity was found to be of the order of several Omega cm at room temperature in two terminal measurements.

Peptide-equipped tobacco mosaic virus templates for selective and controllable biomineral deposition

Summary The coating of regular-shaped, readily available nanorod biotemplates with inorganic compounds has attracted increasing interest during recent years. The goal is an effective, bioinspired fabrication of fiber-reinforced composites and robust, miniaturized technical devices. Major challenges in the synthesis of applicable mineralized nanorods lie in selectivity and adjustability of the inorganic material deposited on the biological, rod-shaped backbones, with respect to thickness and surface profile of the resulting coating, as well as the avoidance of aggregation into extended superstructures. Nanotubular tobacco mosaic virus (TMV) templates have proved particularly suitable towards this goal: Their multivalent protein coating can be modified by high-surface-density conjugation of peptides, inducing and governing silica deposition from precursor solutions in vitro. In this study, TMV has been equipped with mineralization-directing peptides designed to yield silica coatings in a reliable and predictable manner via precipitation from tetraethoxysilane (TEOS) precursors. Three peptide groups were compared regarding their influence on silica polymerization: (i) two peptide variants with alternating basic and acidic residues, i.e. lysine–aspartic acid (KD)x motifs expected to act as charge-relay systems promoting TEOS hydrolysis and silica polymerization; (ii) a tetrahistidine-exposing polypeptide (CA4H4) known to induce silicification due to the positive charge of its clustered imidazole side chains; and (iii) two peptides with high ZnO binding affinity. Differential effects on the mineralization of the TMV surface were demonstrated, where a (KD)x charge-relay peptide (designed in this study) led to the most reproducible and selective silica deposition. A homogenous coating of the biotemplate and tight control of shell thickness were achieved.

Tailoring the surface properties of tobacco mosaic virions by the integration of bacterially expressed mutant coat protein

Due to its small dimensions and high stability, tobacco mosaic virus (TMV) is used as nano-scaffold frequently. Its surface can be engineered to meet specific needs for technical, medical or materials applications. However, not all technically desirable TMV coat protein (CP) mutants can be propagated in plants successfully, if they change the efficiency of virion assembly. In order to circumvent this problem, a novel wild type (wt) CP-assisted and RNA-directed assembly procedure was designed for a recalcitrant CP mutant: Although pure hexahistidine-tagged CP cannot form particles on its own with TMV RNA in vitro, it was integrated into full-length particles if blended with wt CP in different proportions. The resulting rods formed dense monolayers with short range alignment on silicon substrates, substantially different from the largely wavy patterns obtained with wt TMV. Since they also mediated efficient ZnO deposition under mild conditions, the approach has yielded a new class of biotemplates which are amenable to the formation of nanostructured hybrid materials with adjustable texture for various applications.

Genetically improved monolayer-forming tobacco mosaic viruses to generate nanostructured semiconducting bio/inorganic hybrids.

The genetically determined design of structured functional bio/inorganic materials was investigated by applying a convective assembly approach. Wildtype tobacco mosaic virus (wt TMV) as well as several TMV mutants were organized on substrates over macroscopic-length scales. Depending on the virus type, the self-organization behavior showed pronounced differences in the surface arrangement under the same convective assembly conditions. Additionally, under varying assembly parameters, the virus particles generated structures encompassing morphologies emerging from single micrometer long fibers aligned parallel to the triple-contact line through disordered but dense films to smooth and uniform monolayers. Monolayers with diverse packing densities were used as templates to form TMV/ZnO hybrid materials. The semiconducting properties can be directly designed and tuned by the variation of the template architecture which are reflected in the transistor performance.

Functional tethered bilayer membranes as a biosensor platform

Tethered bilayer lipid membranes (tBLMs) present a powerful kind of solid supported membranes that can be used to study membrane related processes. TBLMs offer a quasi-natural environment where membrane proteins can be embedded and investigated. A tBLM consists of a lipid bilayer that is coupled covalently via a spacer group to a solid support. This being an electrode, electrical characterization of the system is possible and potential bio-sensing applications arise. We have developed a whole series of tBLM systems that provide different spacer groups and have anchor groups to allow for the assembly either on gold or on oxide surfaces. They show excellent barrier properties in terms of electrical resistance and capacitance. Systems are characterized using a variety of surface analytical tools. Here, we present the incorporation of the ion carrier valinomycin into a membrane consisting of a new anchor lipid (DPTT). This molecule is a modification of a previously reported structure. The modification is based on a new generic approach in the synthesis, which allows for an easier access different molecules and is open to adaptation to various substrates

Piezoelectric Templates - New Views on Biomineralization and Biomimetics.

Biomineralization in general is based on electrostatic interactions and molecular recognition of organic and inorganic phases. These principles of biomineralization have also been utilized and transferred to bio-inspired synthesis of functional materials during the past decades. Proteins involved in both, biomineralization and bio-inspired processes, are often piezoelectric due to their dipolar character hinting to the impact of a template’s piezoelectricity on mineralization processes. However, the piezoelectric contribution on the mineralization process and especially the interaction of organic and inorganic phases is hardly considered so far. We herein report the successful use of the intrinsic piezoelectric properties of tobacco mosaic virus (TMV) to synthesize piezoelectric ZnO. Such films show a two-fold increase of the piezoelectric coefficient up to 7.2 pm V−1 compared to films synthesized on non-piezoelectric templates. By utilizing the intrinsic piezoelectricity of a biotemplate, we thus established a novel synthesis pathway towards functional materials, which sheds light on the whole field of biomimetics. The obtained results are of even broader and general interest since they are providing a new, more comprehensive insight into the mechanisms involved into biomineralization in living nature.

Template-controlled mineralization: Determining film granularity and structure by surface functionality patterns.

Summary We present a promising first example towards controlling the properties of a self-assembling mineral film by means of the functionality and polarity of a substrate template. In the presented case, a zinc oxide film is deposited by chemical bath deposition on a nearly topography-free template structure composed of a pattern of two self-assembled monolayers with different chemical functionality. We demonstrate the template-modulated morphological properties of the growing film, as the surface functionality dictates the granularity of the growing film. This, in turn, is a key property influencing other film properties such as conductivity, piezoelectric activity and the mechanical properties. A very pronounced contrast is observed between areas with an underlying fluorinated, low energy template surface, showing a much more (almost two orders of magnitude) coarse-grained film with a typical agglomerate size of around 75 nm. In contrast, amino-functionalized surface areas induce the growth of a very smooth, fine-grained surface with a roughness of around 1 nm. The observed influence of the template on the resulting clear contrast in morphology of the growing film could be explained by a contrast in surface adhesion energies and surface diffusion rates of the nanoparticles, which nucleate in solution and subsequently deposit on the functionalized substrate.

Semiconducting Hybrid Layer Fabrication Scaffolded by Virus Shells

The formation of virus-based semiconducting hybrid thin films is a two-step process, which involves assembly of virus particles as a template layer and subsequent selective mineralization of the virus surface with inorganic nanoparticles to build a semiconducting organic-inorganic hybrid film. Here, we present the use of the convective assembly technique to obtain homogeneous and dense template monolayers of wild-type tobacco mosaic virus (wt-TMV) and the TMV mutant E50Q, of which most particles do not have detectable amounts of RNA in the protein tube. On the top of the aligned virus layer, zinc oxide (ZnO) is deposited to prepare virus-ZnO semiconducting hybrid films with controllable thickness under mild conditions of the chemical bath deposition (CBD).

Controllable Virus-Directed Synthesis of Nanostructured Hybrids Induced by Organic/Inorganic Interactions

The bioinspired synthesis of hierarchical hybrid nanomaterials using biological objects as a template attracts growing interest for the design of new technologically relevant nanostructured materials. To ensure control over the shape and properties of the fabricated hybrid structures, understanding of the growth mechanism is required. In this work, tobacco mosaic virus (TMV) is used as a template to direct the synthesis of zinc sulfide (ZnS) at ambient conditions and different pH from additive‐free aqueous solution. TMV/ZnS hybrid nanowires or thin films are obtained with controllable thickness of the inorganic layer. The deposition mechanism is studied by monitoring the optical properties, band gap (Eg) and particle size, respectively, of ZnS particles mineralized on the TMV template and ZnS reference nanoparticles. A heterogeneous nucleation of the inorganic phase on the template surface is proposed. Band gap measurements reveal that the average size of the ZnS nanoparticles grown on the virus surface is smaller compared to solution‐grown nanoparticles. Moreover, a blue shift of the ZnS photoluminescence peak indicates a dominance of different crystal lattice defects in both systems. The present method for the selective template‐directed mineralization opens new possibilities in the synthesis of well‐organized functional hybrid materials.