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Metal-mediated base pairing of DNA has been a topic of extensive research spanning over more than four decades. Precise positioning of a single metal ion by predetermining the DNA sequence, as well as improved conductivity offered by the ions, make these structures interesting candidates in the context of using DNA in nanotechnology. Here, we report the formation and characterization of conjugates of long (kilo bases) homoguanine DNA strands with silver ions. We demonstrate using atomic force microscopy (AFM) and scanning tunneling microscope (STM) that binding of silver ions leads to folding of homoguanine DNA strands in a "hairpin" fashion to yield double-helical, left-handed molecules composed of G-G base pairs each stabilized by a silver ion. Further folding of the DNA-silver conjugate yields linear molecules in which the two halves of the double helix are twisted one against the other in a right-handed fashion. Quantum mechanical calculations on smaller molecular models support the helical twist directions obtained by the high resolution STM analysis. These long guanine-based nanostructures bearing a chain of silver ions have not been synthesized and studied before and are likely to possess conductive properties that will make them attractive candidates for nanoelectronics.
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Throughout the past few decades, guanine quadruplex DNA structures have attracted much interest both from a fundamental material science perspective and from a technologically oriented perspective. Novel guanine octuplex DNA, formed from coiled quadruplex DNA, was recently discovered as a stable and rigid DNA-based nanostructure. A detailed electronic structure study of this new nanomaterial, performed by scanning tunneling spectroscopy on a subsingle-molecule level at cryogenic temperature, is presented herein. The electronic levels and lower energy gap of guanine octuplex DNA compared to quadruplex DNA dictate higher transverse conductivity through guanine octads than through guanine tetrads.
Assuntos
Quadruplex G , Nanoestruturas , DNA/química , Eletrônica , Guanina , Conformação de Ácido NucleicoRESUMO
Condensation and remodeling of nuclear genomes play an essential role in the regulation of gene expression and replication. Yet, our understanding of these processes and their regulatory role in other DNA-containing organelles, has been limited. This study focuses on the packaging of kinetoplast DNA (kDNA), the mitochondrial genome of kinetoplastids. Severe tropical diseases, affecting large human populations and livestock, are caused by pathogenic species of this group of protists. kDNA consists of several thousand DNA minicircles and several dozen DNA maxicircles that are linked topologically into a remarkable DNA network, which is condensed into a mitochondrial nucleoid. In vitro analyses implicated the replication protein UMSBP in the decondensation of kDNA, which enables the initiation of kDNA replication. Here, we monitored the condensation of kDNA, using fluorescence and atomic force microscopy. Analysis of condensation intermediates revealed that kDNA condensation proceeds via sequential hierarchical steps, where multiple interconnected local condensation foci are generated and further assemble into higher order condensation centers, leading to complete condensation of the network. This process is also affected by the maxicircles component of kDNA. The structure of condensing kDNA intermediates sheds light on the structural organization of the condensed kDNA network within the mitochondrial nucleoid.
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Replicação do DNA/genética , DNA de Cinetoplasto/metabolismo , DNA Mitocondrial/genética , Núcleo Celular/metabolismo , Crithidia fasciculata/genética , DNA/metabolismo , DNA Circular/metabolismo , DNA de Cinetoplasto/genética , Proteínas de Ligação a DNA/genética , Genoma Mitocondrial/genética , Mitocôndrias/metabolismoRESUMO
Guanine quadruplex (G4)-DNA structures have sparked the interest of many scientists due to their important biological roles and their potential use in molecular nanoelectronics and nanotechnology. The high guanine content in G4-DNA endows it with mechanical stability, robustness, and improved charge transport properties-attractive attributes for a molecular nanowire. The self-driven formation of a novel G4-DNA-based nanostructure, coined guanine octuplex (G8)-DNA, is reported herein. Atomic force microscopy and scanning tunneling microscopy characterization of this molecule reveal its organized coiled-coil structure, which is found to be stable under different temperatures and surrounding conditions. G8-DNA exhibits enhanced stiffness, mechanical and thermodynamic stability when compared to its parent G4-DNA. These, along with its high guanine content, make G8-DNA a compelling new molecule, and a highly prospective candidate for molecular nanoelectronics.
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DNA/química , Quadruplex G , Nanotecnologia , NanoestruturasRESUMO
Understanding charge transport in DNA molecules is a long-standing problem of fundamental importance across disciplines1,2. It is also of great technological interest due to DNA's ability to form versatile and complex programmable structures. Charge transport in DNA-based junctions has been reported using a wide variety of set-ups2-4, but experiments so far have yielded seemingly contradictory results that range from insulating5-8 or semiconducting9,10 to metallic-like behaviour11. As a result, the intrinsic charge transport mechanism in molecular junction set-ups is not well understood, which is mainly due to the lack of techniques to form reproducible and stable contacts with individual long DNA molecules. Here we report charge-transport measurements through single 30-nm-long double-stranded DNA (dsDNA) molecules with an experimental set-up that enables us to address individual molecules repeatedly and to measure the current-voltage characteristics from 5 K up to room temperature. Strikingly, we observed very high currents of tens of nanoamperes, which flowed through both homogeneous and non-homogeneous base-pair sequences. The currents are fairly temperature independent in the range 5-60 K and show a power-law decrease with temperature above 60 K, which is reminiscent of charge transport in organic crystals. Moreover, we show that the presence of even a single discontinuity ('nick') in both strands that compose the dsDNA leads to complete suppression of the current, which suggests that the backbones mediate the long-distance conduction in dsDNA, contrary to the common wisdom in DNA electronics2-4.
Assuntos
DNA/química , Condutividade Elétrica , Ouro/química , Nanoestruturas/química , Pareamento de Bases , Dimerização , Eletrônica , Elétrons , Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Modelos Moleculares , Nanoestruturas/ultraestrutura , Conformação de Ácido NucleicoRESUMO
Metal-mediated base-paired DNA has long been investigated for basic scientific pursuit and for nanoelectronics purposes. Particularly attractive in these domains is the Ag+-intercalated polycytosine DNA duplex. Extensive studies of this molecule have led to our current understanding of its self-assembly properties, high thermodynamic and structural stability, and high longitudinal conductivity. However, a high-resolution morphological characterization of long Ag+-intercalated polycytosine DNA has hitherto not been carried out. Furthermore, the electronic level structure of this molecule has not been studied before. Here we present a scanning tunneling microscopy and spectroscopy study of this intriguing nanowire. Its temperature-independent morphological and electronic properties suggest substantial stability, while its emergent electronic levels and energy gap provide the basis for its high conductivity.
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Pareamento de Bases , DNA , Nanofios , Prata , Citosina , DNA/química , EletrônicaRESUMO
Nanopores have become an important tool for the detection and analysis of molecules at the single-molecule level. Surface modification of solid-state nanopores can improve their durability and efficiency. Peptides are ideal for surface modifications as they allow tailoring of multiple properties by a rational design of their sequence. Here, silicon nitride nanopores were coated by a dipeptide layer where a l-3,4-dihydroxyphenylalanine (DOPA) residue is the anchoring element and the other amino acid moiety is the functional element. DOPA binds tightly to many types of surfaces and allows a one-step functionalization of surfaces by simple immersion. As a result, the lifetime of coated nanopores increased from hours to months and the current-stability has significantly improved with respect to uncoated pores. This improvement is achieved by controlling the surface wettability and charge. Peptide-coated nanopores can be utilized as sensitive sensors that can be adjusted based on the choice of the functional moiety of the coated peptide. In addition, the coating slows down dsDNA translocation because of the DNA interaction with the pore coating.
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Di-Hidroxifenilalanina/química , Dipeptídeos/química , Nanoporos/ultraestrutura , Nanotecnologia , DNA/efeitos dos fármacos , Dipeptídeos/genética , Compostos de Silício/química , Propriedades de Superfície/efeitos dos fármacosRESUMO
Perovskite nanostructures have attracted much attention in recent years due to their suitability for a variety of applications such as photovoltaics, light-emitting diodes (LEDs), nanometer-size lasing, and more. These uses rely on the conductive properties of these nanostructures. However, electrical characterization of individual, thin perovskite nanowires has not yet been reported. Here, conductive atomic force microscopy characterization of individual cesium lead halide nanowires is presented. Clear differences are observed in the conductivity of nanowires containing only bromide and nanowires containing a mixture of bromide and iodide. The differences are attributed to a higher density of crystalline defects, deeper trap states, and higher inherent conductivity for nanowires with mixed bromide-iodide content.
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Understanding the effect of external conditions, temperature in particular, on novel nanomaterials is of great significance. The powerful ability of scanning tunneling microscopy (STM) to characterize topography and electronic levels on a single molecule scale is utilized herein to characterize individual silver-containing poly(dG)-poly(dC) DNA molecules, at different temperatures. These measurements indicate that the molecule is a truly hybrid metal-organic nanomaterial with electronic states originating from both the DNA and the embedded silver. The temperature dependence of this density of states (DOS) leads to the temperature dependent STM apparent height of the molecule-a phenomenon that has not been observed before for other complex nanostructures.
Assuntos
DNA , Microscopia de Tunelamento , Nanoestruturas , Prata , Temperatura , DNA/química , DNA/ultraestrutura , Eletrônica , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Poli C/química , Poli G/química , Prata/químicaRESUMO
The quest for a suitable molecule to pave the way to molecular nanoelectronics has been met with obstacles for over a decade. Candidate molecules such as carbon nanotubes lack the appealing trait of self-assembly, while DNA seems to lack the desirable feature of conductivity. Silver-containing poly(dG)-poly(dC) DNA (E-DNA) molecules have recently been reported as promising candidates for molecular electronics, owing to the selectivity of their metallization, their thin and uniform structure, their resistance to deformation, and their maximum possible high conductivity. Ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) of E-DNA presents an elaborate high-resolution morphology characterization of these unique molecules, along with a detailed depiction of their electronic level structure. The energy levels found for E-DNA indicate a novel truly hybrid metal-molecule structure, potentially more conductive than other DNA-based alternatives.
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DNA/química , Microscopia de Tunelamento , Poli G/química , Prata/química , Análise Espectral , Poli C/químicaRESUMO
The rapid growth in demand for data and the emerging applications of Big Data require the increase of memory capacity. Magnetic memory devices are among the leading technologies for meeting this demand; however, they rely on the use of ferromagnets that creates size reduction limitations and poses complex materials requirements. Usually magnetic memory sizes are limited to 30-50 nm. Reducing the size even further, to the ≈10-20 nm scale, destabilizes the magnetization and its magnetic orientation becomes susceptible to thermal fluctuations and stray magnetic fields. In the present work, it is shown that 10 nm single domain ferromagnetism can be achieved. Using asymmetric adsorption of chiral molecules, superparamagnetic iron oxide nanoparticles become ferromagnetic with an average coercive field of ≈80 Oe. The asymmetric adsorption of molecules stabilizes the magnetization direction at room temperature and the orientation is found to depend on the handedness of the chiral molecules. These studies point to a novel method for the miniaturization of ferromagnets (down to ≈10 nm) using established synthetic protocols.
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Charge transport through molecular structures is interesting both scientifically and technologically. To date, DNA is the only type of polymer that transports significant currents over distances of more than a few nanometers in individual molecules. For molecular electronics, DNA derivatives are by far more promising than native DNA due to their improved charge-transport properties. Here, the synthesis of several unique DNA derivatives along with electrical characterization and theoretical models is surveyed. The derivatives include double stranded poly(G)-poly(C) DNA molecules, four stranded G4-DNA, metal-DNA hybrid molecular wires, and other DNA molecules that are modified either at the bases or at the backbone. The electrical characteristics of these nanostructures, studied experimentally by electrostatic force microscopy, conductive atomic force microscopy, and scanning tunneling microscopy and spectroscopy, are reviewed.
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DNA/química , DNA/síntese química , Equipamentos e Provisões Elétricas , Metais/síntese química , Metais/químicaRESUMO
There is an increasing demand for the development of a simple Si-based universal memory device at the nanoscale that operates at high frequencies. Spin-electronics (spintronics) can, in principle, increase the efficiency of devices and allow them to operate at high frequencies. A primary challenge for reducing the dimensions of spintronic devices is the requirement for high spin currents. To overcome this problem, a new approach is presented that uses helical chiral molecules exhibiting spin-selective electron transport, which is called the chiral-induced spin selectivity (CISS) effect. Using the CISS effect, the active memory device is miniaturized for the first time from the micrometer scale to 30 nm in size, and this device presents memristor-like nonlinear logic operation at low voltages under ambient conditions and room temperature. A single nanoparticle, along with Au contacts and chiral molecules, is sufficient to function as a memory device. A single ferromagnetic nanoplatelet is used as a fixed hard magnet combined with Au contacts in which the gold contacts act as soft magnets due to the adsorbed chiral molecules.
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Over the past decades, DNA, the carrier of genetic information, has been used by researchers as a structural template material. Watson-Crick base pairing enables the formation of complex 2D and 3D structures from DNA through self-assembly. Various methods have been developed to functionalize these structures for numerous utilities. Metallization of DNA has attracted much attention as a means of forming conductive nanostructures. Nevertheless, most of the metallized DNA wires reported so far suffer from irregularity and lack of end-to-end electrical connectivity. An effective technique for formation of thin gold-coated DNA wires that overcomes these drawbacks is developed and presented here. A conductive atomic force microscopy setup, which is suitable for measuring tens to thousands of nanometer long molecules and wires, is used to characterize these DNA-based nanowires. The wires reported here are the narrowest gold-coated DNA wires that display long-range conductivity. The measurements presented show that the conductivity is limited by defects, and that thicker gold coating reduces the number of defects and increases the conductive length. This preparation method enables the formation of molecular wires with dimensions and uniformity that are much more suitable for DNA-based molecular electronics.
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Nanofios , DNA , Ouro , Microscopia de Força Atômica , NanoestruturasRESUMO
There is an increasing demand for realizing a simple Si based universal memory device working at ambient temperatures. In principle, nonvolatile magnetic memory can operate at low power consumption and high frequencies. However, in order to compete with existing memory technology, size reduction and simplification of the used material systems are essential. In this work, the chiral-induced spin selectivity effect is used along with 30-50 nm ferromagnetic nanoplatelets in order to realize a simple magnetic memory device. The vertical memory is Si compatible, easy to fabricate, and in principle can be scaled down to a single nanoparticle size. Results show clear dual magnetization behavior with threefold enhancement between the one and zero states. The magnetization of the device is accompanied with large avalanche like noise that is ascribed to the redistribution of current densities due to spin accumulation inducing coupling effects between the different nanoplatelets.
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Perovskite nanostructures, both hybrid organo-metal and fully inorganic perovskites, have gained a lot of interest in the past few years for their intriguing optical properties in the visible region. We report on inorganic cesium lead bromide (CsPbBr3) nanowires (NWs) having quantum confined dimensions corresponding to 5 unit cells. The addition of various hydrohalic acids (HX, X = Cl, Br, I) was found to highly affect the NW length, composition, and optical properties. Hydrochloric (HCl) and hydroiodic (HI) acids mixed in the reaction solution influence the crystal structure and optical properties and shorten the NWs, while the hydrobromic acid (HBr) addition results solely in shorter NWs, without any structural change. The addition of HX increases the acidity of the reaction solution, resulting in protonation of the oleylamine ligands from oleylamine into oleyl-ammonium cations that behave similarly to Cs+ during crystallization. Therefore, the positions of the Cs+ at the growing surface of the NWs are taken by the oleyl-ammonium cations, thus blocking further growth in the favored direction. The emission of the NWs is tunable between â¼423-505 nm and possesses a potential in the optoelectronic field. Moreover, electrical conductivity measurements of the NWs are discussed to give a new point of view regarding the conductivity of perovskite nanostructures.
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We describe the detailed microscopic changes in a peptide monolayer following kinase-mediated phosphorylation. A reversible electrochemical transformation was observed using square wave voltammetry (SWV) in the reversible cycle of peptide phosphorylation by ERK2 followed by dephosphorylation by alkaline phosphatase. A newly developed method for analyzing local roughness, measured by atomic force microscope (AFM), showed a bimodal distribution. This may indicate either a hole-formation mechanism and/or regions on the surface in which the peptide changed its conformation upon phosphorylation, resulting in increased roughness and current. Our results provide the mechanistic basis for developing biosensors for detecting kinase-mediated phosphorylation in disease.
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Microscopia de Força Atômica/métodos , Proteína Quinase 1 Ativada por Mitógeno/metabolismo , Peptídeos/química , Fosfatase Alcalina/metabolismo , Eletroquímica , FosforilaçãoRESUMO
Mimicking the multifunctional bacterial type IV pili (T4Ps) nanofibres provides an important avenue towards the development of new functional nanostructured biomaterials. Yet, the development of T4Ps-based applications is limited by the inability to form these nanofibres in vitro from their pilin monomers. Here, to overcome this limitation, we followed a reductionist approach and designed a self-assembling pilin-based 20-mer peptide, derived from the presumably bioelectronic pilin of Geobacter sulfurreducens. The designed 20-mer, which spans sequences from both the polymerization domain and the functionality region of the pilin, self-assembled into ordered nanofibres. Investigation of the 20-mer revealed that shorter sequences which correspond to the polymerization domain form a supramolecular ß-sheet, contrary to their helical configuration in the native T4P core, due to alternative molecular recognition. In contrast, the sequence derived from the functionality region maintains a native-like, helical conformation. This study presents a new family of self-assembling peptides which form T4P-like nanostructures.
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Fímbrias Bacterianas/química , Geobacter/fisiologia , Nanofibras/química , Peptídeos/química , Cristalografia por Raios XRESUMO
D. Porath, A. Kotlyar, and co-workers transform DNA to a conducting material by metalization through coating or chemical modifications, as described on page 4839. Specific and reversible metalization of poly(dG)-poly(dC) DNA by migration of atoms from silver nanoparticles to the DNA is demonstrated. As the transformation occurs gradually, novel, truly hybrid molecular structures are obtained, paving the way to their usage as nanowires in programmable molecular electronic devices and circuits.
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DNA/química , Prata/química , Nanopartículas Metálicas/química , Nanofios/químicaRESUMO
Migration of silver atoms from silver nano-particles selectively to a double-stranded poly(dG)-poly(dC) polymer leads to metallization of the DNA. As a result the DNA molecules become shorter and thicker (higher), as evident from the atomic force microscopy imaging analysis. The metalized molecules can be detected by transmission and scanning electron microscopy in contrast to the initial non-metalized ones.