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Motivated by observations of cell orientation at biofilm-substrate interfaces and reports that cell orientation and adhesion play important roles in biofilm evolution and function, we investigated the influence of surface chemistry on the orientation of Escherichia coli cells captured from flow onto surfaces that were cationic, hydrophobic, or anionic. We characterized the initial orientations of nonmotile cells captured from gentle shear relative to the surface and flow directions. The broad distribution of captured cell orientations observed on cationic surfaces suggests that rapid electrostatic attractions of cells to oppositely charged surfaces preserve the instantaneous orientations of cells as they rotate in the near-surface shearing flow. By contrast, on hydrophobic and anionic surfaces, cells were oriented slightly more in the plane of the surface and in the flow direction compared with that on the cationic surface. This suggests slower development of adhesion at hydrophobic and anionic surfaces, allowing cells to tip toward the surface as they adhere. Once cells were captured, the flow was increased by 20-fold. Cells did not reorient substantially on the cationic surface, suggesting a strong cell-surface bonding. By contrast, on hydrophobic and anionic surfaces, increased shear forced cells to tip toward the surface and align in the flow direction, a process that was reversible upon reducing the shear. These findings suggest mechanisms by which surface chemistry may play a role in the evolving structure and function of microbial communities.

Bacterial swimming in flow near surfaces is critical to the spread of infection and device colonization. Understanding how material properties affect flagella- and motility-dependent bacteria-surface interactions is a first step in designing new medical devices that mitigate the risk of infection. We report that, on biomaterial coatings such as polyethylene glycol (PEG) hydrogels and end-tethered layers that prevent adhesive bacteria accumulation, the coating mechanics and hydration control the near-surface travel and dynamic surface contact of E. coli cells in gentle shear flow (order 10 s -1 ). Along relatively stiff (order 1 MPa) PEG hydrogels or end-tethered layers of PEG chains of similar polymer correlation length, run-and-tumble E. coli travel nanometrically close to the coating's surface in the flow direction in distinguishable runs or "engagements" that persist for several seconds, after which cells leave the interface. The duration of these engagements was greater along stiff hydrogels and end-tethered layers compared with softer, more-hydrated hydrogels. Swimming cells that left stiff hydrogels or end-tethered layers proceeded out to distances of a few microns and then returned to engage the surface again and again, while cells engaging the soft hydrogel tended not to return after leaving. As a result of differences in the duration of engagements and tendency to return to stiff hydrogel and end-tethered layers, swimming E. coli experienced 3 times the integrated dynamic surface contact with stiff coatings compared with softer hydrogels. The striking similarity of swimming behaviors near 16-nm-thick end-tethered layers and 100-μm-thick stiff hydrogels argues that only the outermost several nanometers of a highly hydrated coating influence cell travel. The range of material stiffnesses, cell-surface distance during travel, and time scales of travel compared with run-and-tumble time scales suggests the influence of the coating derives from its interactions with flagella and its potential to alter flagellar bundling. Given that restriction of flagellar rotation is known to trigger increased virulence, bacteria influenced by surfaces in one region may become predisposed to form a biofilm downstream.

Genetic modification to add tryptophan to PilA, the monomer for the electrically conductive pili of Geobacter sulfurreducens, yields conductive protein filaments 2000-fold more conductive than the wild-type pili while cutting the diameter in half to 1.5 nm., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Studies on the mechanisms for extracellular electron transfer in Geobacter species have primarily focused on Geobacter sulfurreducens, but the poor conservation of genes for some electron transfer components within the Geobacter genus suggests that there may be a diversity of extracellular electron transport strategies among Geobacter species. Examination of the gene sequences for PilA, the type IV pilus monomer, in Geobacter species revealed that the PilA sequence of Geobacter uraniireducens was much longer than that of G. sulfurreducens. This is of interest because it has been proposed that the relatively short PilA sequence of G. sulfurreducens is an important feature conferring conductivity to G. sulfurreducens pili. In order to investigate the properties of the G. uraniireducens pili in more detail, a strain of G. sulfurreducens that expressed pili comprised the PilA of G. uraniireducens was constructed. This strain, designated strain GUP, produced abundant pili, but generated low current densities and reduced Fe(III) very poorly. At pH 7, the conductivity of the G. uraniireducens pili was 3 × 10(-4) S/cm, much lower than the previously reported 5 × 10(-2) S/cm conductivity of G. sulfurreducens pili at the same pH. Consideration of the likely voltage difference across pili during Fe(III) oxide reduction suggested that G. sulfurreducens pili can readily accommodate maximum reported rates of respiration, but that G. uraniireducens pili are not sufficiently conductive to be an effective mediator of long-range electron transfer. In contrast to G. sulfurreducens and G. metallireducens, which require direct contact with Fe(III) oxides in order to reduce them, G. uraniireducens reduced Fe(III) oxides occluded within microporous beads, demonstrating that G. uraniireducens produces a soluble electron shuttle to facilitate Fe(III) oxide reduction. The results demonstrate that Geobacter species may differ substantially in their mechanisms for long-range electron transport and that it is important to have information beyond a phylogenetic affiliation in order to make conclusions about the mechanisms by which Geobacter species are transferring electrons to extracellular electron acceptors.

Solar cells fabricated using alkyl ammonium metal halides as light absorbers have the right combination of high power conversion efficiency and ease of fabrication to realize inexpensive but efficient thin film solar cells. However, they degrade under prolonged exposure to sunlight. Herein, we show that this degradation is quasi-reversible, and that it can be greatly lessened by simple modifications of the solar cell operating conditions. We studied perovskite devices using electrochemical impedance spectroscopy (EIS) with methylammonium (MA)-, formamidinium (FA)-, and MA(x)FA(1-x) lead triiodide as active layers. From variable temperature EIS studies, we found that the diffusion coefficient using MA ions was greater than when using FA ions. Structural studies using powder X-ray diffraction (PXRD) show that for MAPbI3 a structural change and lattice expansion occurs at device operating temperatures. On the basis of EIS and PXRD studies, we postulate that in MAPbI3 the predominant mechanism of accelerated device degradation under sunlight involves thermally activated fast ion transport coupled with a lattice-expanding phase transition, both of which are facilitated by absorption of the infrared component of the solar spectrum. Using these findings, we show that the devices show greatly improved operation lifetimes and stability under white-light emitting diodes, or under a solar simulator with an infrared cutoff filter or with cooling.

Thiol (-SH) groups within a Zr(IV)-based metal-organic framework (MOF) anchor Hg(II) atoms; oxidation by H2O2 then leads to acidic sulfonate functions for catalyzing acetylene hydration at room temperature.

Unlabelled: Direct measurement of multiple physical properties of Geobacter sulfurreducens pili have demonstrated that they possess metallic-like conductivity, but several studies have suggested that metallic-like conductivity is unlikely based on the structures of the G. sulfurreducens pilus predicted from homology models. In order to further evaluate this discrepancy, pili were examined with synchrotron X-ray microdiffraction and rocking-curve X-ray diffraction. Both techniques revealed a periodic 3.2-Å spacing in conductive, wild-type G. sulfurreducens pili that was missing in the nonconductive pili of strain Aro5, which lack key aromatic acids required for conductivity. The intensity of the 3.2-Å peak increased 100-fold when the pH was shifted from 10.5 to 2, corresponding with a previously reported 100-fold increase in pilus conductivity with this pH change. These results suggest a clear structure-function correlation for metallic-like conductivity that can be attributed to overlapping π-orbitals of aromatic amino acids. A homology model of the G. sulfurreducens pilus was constructed with a Pseudomonas aeruginosa pilus model as a template as an alternative to previous models, which were based on a Neisseria gonorrhoeae pilus structure. This alternative model predicted that aromatic amino acids in G. sulfurreducens pili are packed within 3 to 4 Å, consistent with the experimental results. Thus, the predictions of homology modeling are highly sensitive to assumptions inherent in the model construction. The experimental results reported here further support the concept that the pili of G. sulfurreducens represent a novel class of electronically functional proteins in which aromatic amino acids promote long-distance electron transport., Importance: The mechanism for long-range electron transport along the conductive pili of Geobacter sulfurreducens is of interest because these "microbial nanowires" are important in biogeochemical cycling as well as applications in bioenergy and bioelectronics. Although proteins are typically insulators, G. sulfurreducens pilus proteins possess metallic-like conductivity. The studies reported here provide important structural insights into the mechanism of the metallic-like conductivity of G. sulfurreducens pili. This information is expected to be useful in the design of novel bioelectronic materials., (Copyright © 2015 Malvankar et al.)

The nanoscale imaging of charge flow in proteins is crucial to understanding several life processes, including respiration, metabolism and photosynthesis. However, existing imaging methods are only effective under non-physiological conditions or are limited to photosynthetic proteins. Here, we show that electrostatic force microscopy can be used to directly visualize charge propagation along pili of Geobacter sulfurreducens with nanometre resolution and under ambient conditions. Charges injected at a single point into individual, untreated pili, which are still attached to cells, propagated over the entire filament. The mobile charge density in the pili, as well as the temperature and pH dependence of the charge density, were similar to those of carbon nanotubes and other organic conductors. These findings, coupled with a lack of charge propagation in mutated pili that were missing key aromatic amino acids, suggest that the pili of G. sulfurreducens function as molecular wires with transport via delocalized charges, rather than the hopping mechanism that is typical of biological electron transport.

Colloidal assembly of nC60 fullerene with naturally abundant magnetic iron oxide NPs will affect their fate and transformation in environmental media. In solution, fullerene association to aggregating iron oxide NPs/clusters greatly enhanced the overall colloidal stability. Development of depletion-mediated structured fullerene layers between pure and surface modified γFe2O3 NPs possibly resulted in such stabilization. Here, we also report that on air-water interface, association of fullerene to pure and humic acid (HA7) coated γFe2O3 NPs led to the formation of ordered assemblies, e.g., binary wires and closed-packed "crystalline" and "glassy" structures in the presence and absence of electrolytes suggesting immobilization of the former. The interaction of fullerene to Fe3O4 NPs and clusters also produced ordered assemblies along with amorphous aggregates. Fullerene interaction with Fe3O4 NPs in low concentration of HA1 and Na(+) at pH 6 formed dendritic growth and polycrystalline circular assemblies on air-water interface. HRTEM study further revealed that the monolayer circular assemblies were highly ordered but structural degeneracy was evident in multilayers. Therefore, interfacial assemblies of fullerene with iron oxide NPs resulted in short-range periodic structures with concomitant immobilization and reduction in availability of the former, especially in soils or sediments rich in the latter.

We describe the spontaneous assembly of ligand-stabilized gold nanoparticles on the surfaces of gallium droplets in suspension. By subsequent deposition of these coated droplets onto substrates with patterned electrodes, we form devices that have controlled architecture on the nanometer scale, which allows control of electron transport. In particular, we show that microscopic droplets can be brought into contact with one another with a monolayer of nanoparticles between them, resulting in a junction where electron transport is limited by the Coulomb blockade effect. We characterize the gallium surfaces by optical and electron microscopy and measurement of the interfacial tension. We measure the current-voltage characteristics of devices consisting of one or more Ga droplets and nanoparticle layers in series. The results agree well with the conventional theory of the Coulomb blockade and show how this approach could be used to form hierarchically structured electronic devices.

Here we demonstrate patterning of protein/quantum dot hybrid bionanostructures via electrostatic assembly of engineered negatively charged fluorescent protein with positively charged CdSe/ZnS QD patterns formed through e-beam lithography and post-patterning modification with cationic ligands.

It was recently shown that block copolymers (BCPs) produced room-temperature ferromagnetic materials (RTFMs) due to their nanoscopic ordering and the cylindrical phase yielded the highest coercivity. Here, a series of metal-containing block-random copolymers composed of an alkyl-functionalized homo block (C(16)) and a random block of cobalt complex- (Co) and ferrocene-functionalized (Fe) units was synthesized via ring-opening metathesis polymerization. Taking advantage of the block-random architecture, the influence of dipolar interactions on the magnetic properties of these nanostructured BCP materials was studied by varying the molar ratio of the Co units to the Fe units, while maintaining the cylindrical phase-separated morphology. DC magnetic measurements, including magnetization versus field, zero-field-cooled, and field-cooled, as well as AC susceptibility measurements showed that the magnetic properties of the nanostructured BCP materials could be easily tuned by diluting the cobalt density with Fe units in the cylindrical domains. Decreasing the cobalt density weakened the dipolar interactions of the cobalt nanoparticles, leading to the transition from a room temperature ferromagnetic (RTF) to a superparamagnetic material. These results confirmed that dipolar interactions of the cobalt nanoparticles within the phase-separated domains were responsible for the RTF properties of the nanostructured BCP materials.

Geobacter sulfurreducens can form electrically conductive biofilms, but the potential for conductivity through mixed-species biofilms has not been examined. A current-producing biofilm grown from a wastewater sludge inoculum was highly conductive with low charge transfer resistance even though microorganisms other than Geobacteraceae accounted for nearly half the microbial community.

In this communication, we introduce squaric acid derivatives as anhydrous proton conductors. We report the synthesis, characterization and proton conductivities of four squaric acid derivatives. The anhydrous proton conductivity of one of the derivatives was 2.3 × 10(-3) S cm(-1) at 110 °C, comparable to the conductivity of molten 1H-1,2,3-triazole or 1H-imidazole.

Supercapacitors have attracted interest in energy storage because they have the potential to complement or replace batteries. Here, we report that c-type cytochromes, naturally immersed in a living, electrically conductive microbial biofilm, greatly enhance the device capacitance by over two orders of magnitude. We employ genetic engineering, protein unfolding and Nernstian modeling for in vivo demonstration of charge storage capacity of c-type cytochromes and perform electrochemical impedance spectroscopy, cyclic voltammetry and charge-discharge cycling to confirm the pseudocapacitive, redox nature of biofilm capacitance. The biofilms also show low self-discharge and good charge/discharge reversibility. The superior electrochemical performance of the biofilm is related to its high abundance of cytochromes, providing large electron storage capacity, its nanostructured network with metallic-like conductivity, and its porous architecture with hydrous nature, offering prospects for future low cost and environmentally sustainable energy storage devices., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We demonstrate magnetic switching between two 360° domain wall vortex states in cobalt nanorings, which are candidate magnetic states for robust and low power magnetoresistive random access memory (MRAM) devices. These 360° domain wall (DW) or 'twisted onion' states can have clockwise or counterclockwise circulation, the two states for data storage. Reliable switching between the states is necessary for any realistic device. We accomplish this switching by applying a circular Oersted field created by passing current through a metal atomic force microscope tip placed at the center of the ring. After initializing in an onion state, we rotate the DWs to one side of the ring by passing a current through the center, and can switch between the two twisted states by reversing the current, causing the DWs to split and meet again on the opposite side of the ring. A larger current will annihilate the DWs and create a perfect vortex state in the rings.

Electronic nanostructures made from natural amino acids are attractive because of their relatively low cost, facile processing and absence of toxicity. However, most materials derived from natural amino acids are electronically insulating. Here, we report metallic-like conductivity in films of the bacterium Geobacter sulfurreducens and also in pilin nanofilaments (known as microbial nanowires) extracted from these bacteria. These materials have electronic conductivities of ∼5 mS cm(-1), which are comparable to those of synthetic metallic nanostructures. They can also conduct over distances on the centimetre scale, which is thousands of times the size of a bacterium. Moreover, the conductivity of the biofilm can be tuned by regulating gene expression, and also by varying the gate voltage in a transistor configuration. The conductivity of the nanofilaments has a temperature dependence similar to that of a disordered metal, and the conductivity could be increased by processing.

The dynamic nature of hydrogen bonds in phenolic polymers, where the hydrogen bond donor/acceptor reorientation can occur in a single site, presents lower barriers for proton transport., (This journal is © The Royal Society of Chemistry 2011)

In this communication, we show that liquid crystalline phases lower the activation energy barrier for proton transport. The liquid crystalline phases were obtained using a triphenylene core with alkyl chains bearing a triazole moiety at their termini., (© The Royal Society of Chemistry 2011)

Electron-beam lithography was used to pattern poly(styrene-co-(methyldiaminotriazine) styrene) (PS-Triaz). These polymer nanopatterns were utilized as molecular scaffolds for assembling complementary thymine-functionalized CdSe-ZnS quantum dots (Thy-QDs) via three-point hydrogen-bonding molecular recognition. This interaction was very specific, with N-methyl thymine-functionalized QDs (MeThy-QDs) not depositing on the surfaces. The "lock and key" specificity of the assembly is mirrored in the disassembly process, where complete removal of the QD was observed using a competing thymine guest.

We discuss the coupling between optically excited semiconductor nanocrystals (NC) and thin metal films in both the single and multi-exciton regime. Using time-resolved photoluminescence spectroscopy, we determine the decay dynamics of free space and surface plasmon polariton (SPP) coupled emission. The two dynamics are found to be distinctly different at very small NC-metal separations and at photon energies close to the SPP resonance frequency. A comparison with numerical calculations allow us to conclude that the difference in emission dynamics is associated with the different interactions of parallel and perpendicular dipole emitters with lossy surface waves. Experiments at high excitation densities reveal that the coupling to SPPs and lossy surface waves is identical for excitons and biexcitons.

Transporting protons is essential in several biological processes as well as in renewable energy devices, such as fuel cells. Although biological systems exhibit precise supramolecular organization of chemical functionalities on the nanoscale to effect highly efficient proton conduction, to achieve similar organization in artificial systems remains a daunting challenge. Here, we are concerned with transporting protons on a micron scale under anhydrous conditions, that is proton transfer unassisted by any solvent, especially water. We report that proton-conducting systems derived from facially amphiphilic polymers that exhibit organized supramolecular assemblies show a dramatic enhancement in anhydrous conductivity relative to analogous materials that lack the capacity for self-organization. We describe the design, synthesis and characterization of these macromolecules, and suggest that nanoscale organization of proton-conducting functionalities is a key consideration in obtaining efficient anhydrous proton transport.

We have developed a depth-resolved confocal thermal imaging technique that is capable of measuring the temperature distribution of an encapsulated or semi-obstructed device. The technique employs lock-in charge coupled device-based thermoreflectance imaging via a Nipkow disk confocal microscope, which is used to eliminate extraneous reflections from above or below the imaging plane. We use the confocal microscope to predict the decrease in contrast and dynamic range due to an obstruction for widefield thermoreflectance, and we demonstrate the ability of confocal thermoreflectance to maintain a high contrast and thermal sensitivity in the presence of large reflecting obstructions in the optical path.

We report on the fabrication and optical characterization of dense and ordered arrays of metal nanoparticles. The metal arrays are produced by reducing metal salts in block copolymer (BCP) templates made by solvent annealing of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) or poly(styrene-b-ethylene oxide) (PS-b-PEO) diblock copolymer thin films in mixed solvents. The gold and gold/silver composite nanoparticle arrays show characteristic surface plasmon resonances in the visible wavelength range. The patterning can be applied over large areas onto various substrates. We demonstrate that these metal nanoparticle arrays on metal thin films interact with surface plasmon polaritons (SPPs) that propagate at the film/nanoparticle interface and, therefore, modify the dispersion relation of the SPPs.

A top-down/bottom-up approach is demonstrated by combining electron-beam (e-beam) lithography and a solvent annealing process. Micellar arrays of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with a high degree of lateral order can be produced on a surface where sectoring is defined by e-beam patterning. The e-beam is used to crosslink the block copolymer (BCP) film immediately after spin-coating when the BCP is disordered or in a highly ordered solvent-annealed film. Any patterns can be written into the BCP by crosslinking. Upon exposure to a preferential solvent for the minor component block followed by drying, cylindrical nanopores are generated within the nonexposed areas by a surface reconstruction process, while, in the exposed areas, the films remain unchanged. Nickel nanodot arrays can be placed over selected areas on a surface by thermal evaporation and lift-off process.

We report on radiative decay rate modifications of dipole emitters in the proximity of anisotropic metal nanostructures. Using time, angle, and polarization resolved photoluminescence spectroscopy, we show that resonant interactions between surface plasmons in gold nanodisks and excitons in semiconductor nanocrystals require both spectral and orientational overlap resulting in radiative rate enhancements with directional characteristics. Numerical simulations of emission decay dynamics based on local electric field enhancements are in excellent agreement with experimental results.

We demonstrate a method to fabricate high-quality patterned micelle arrays using poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) block copolymer. Long-range order of the PS-b-P4VP micelle in hexagonal arrays was induced by topographic grating patterns during solvent annealing. The size and row spacing of block copolymer micelle arrays created in this way were uniform. By controlling the thickness of the polymer on the crests and in the troughs of the grating patterns, we prepared PS-b-P4VP micelle arrays having different sizes.

In this paper, we present a simple method to fabricate ultra-high-density hexagonal arrays of ferromagnetic nanorings having 13 nm outer diameter, 5 nm inner diameter and 5 nm thickness. Cobalt magnetic nanorings were fabricated using a self-assembled diblock copolymer template with an angular evaporation of metal followed by an ion-beam etching. Magnetic measurements and theoretical calculations suggest that, at low fields, only the single domain and vortex states are important for rings of this size. The measured magnetization as a function of applied field shows a hysteresis that is consistent. These ultrasmall ferromagnetic rings have potential use in magnetic memory devices due to the simplicity of the preparation coupled with the ultra-high-density and geometry-controlled switching. This fabrication technique can be extended to other materials for applications in optics, sensing and nanoscale research.

Magnetic (FePt) and nonmagnetic (Au) nanoparticles were used to assemble ferritin into near-monodisperse bionanocomposites featuring regular interparticle spacing. The FePt/ferritin assemblies are integrated magnetic materials with ferritin providing added magnetic volume fraction to the magnetic nanocomposite. These assemblies differ from either of their constituent particles in terms of blocking temperature (TB), net magnetic moment, coercivity, and remnance.

Cationic superparamagnetic iron oxide nanoparticles were assembled using a series of anionic polyamidoamine dendrimers. The resulting assemblies featured systematically increasing average interparticle spacing over a 2.4 nm range with increasing dendrimer generation. This increase in spacing modulated the collective magnetic behavior by effective lowering of the dipolar coupling between particles. The results obtained in these studies deviate from the predicted dependence of collective behavior on interparticle spacing, suggesting that a dense assembly of magnetically "free" particles can exist with a surprisingly small space between particles.

Microbes that can transfer electrons to extracellular electron acceptors, such as Fe(iii) oxides, are important in organic matter degradation and nutrient cycling in soils and sediments. Previous investigations on electron transfer to Fe(iii) have focused on the role of outer-membrane c-type cytochromes. However, some Fe(iii) reducers lack c-cytochromes. Geobacter species, which are the predominant Fe(iii) reducers in many environments, must directly contact Fe(iii) oxides to reduce them, and produce monolateral pili that were proposed, on the basis of the role of pili in other organisms, to aid in establishing contact with the Fe(iii) oxides. Here we report that a pilus-deficient mutant of Geobacter sulfurreducens could not reduce Fe(iii) oxides but could attach to them. Conducting-probe atomic force microscopy revealed that the pili were highly conductive. These results indicate that the pili of G. sulfurreducens might serve as biological nanowires, transferring electrons from the cell surface to the surface of Fe(iii) oxides. Electron transfer through pili indicates possibilities for other unique cell-surface and cell-cell interactions, and for bioengineering of novel conductive materials.

We show a simple, robust, chemical route to the fabrication of ultrahigh-density arrays of nanopores with high aspect ratios using the equilibrium self-assembled morphology of asymmetric diblock copolymers. The dimensions and lateral density of the array are determined by segmental interactions and the copolymer molecular weight. Through direct current electrodeposition, we fabricated vertical arrays of nanowires with densities in excess of 1.9 x 10(11) wires per square centimeter. We found markedly enhanced coercivities with ferromagnetic cobalt nanowires that point toward a route to ultrahigh-density storage media. The copolymer approach described is practical, parallel, compatible with current lithographic processes, and amenable to multilayered device fabrication.