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Neurodegenerative diseases, such as Alzheimer’s disease (AD), are associated with protein misfolding and aggregation into amyloid fibrils. Increasing evidence suggests that soluble, low-molecular-weight aggregates play a key role in disease-associated toxicity. Within this population of aggregates, closed-loop pore-like structures have been observed for a variety of amyloid systems, and their presence in brain tissues is associated with high levels of neuropathology. However, their mechanism of formation and relationship with mature fibrils have largely remained challenging to elucidate. Here, we use atomic force microscopy and statistical theory of biopolymers to characterize amyloid ring structures derived from the brains of AD patients. We analyze the bending fluctuations of protofibrils and show that the process of loop formation is governed by the mechanical properties of their chains. We conclude that ex vivo protofibril chains possess greater flexibility than that imparted by hydrogen-bonded networks characteristic of mature amyloid fibrils, such that they are able to form end-to-end connections. These results explain the diversity in the structures formed from protein aggregation and shed light on the links between early forms of flexible ring-forming aggregates and their role in disease.

Neurodegenerative diseases, such as Alzheimer’s Disease (AD), are associated with protein misfolding and aggregation into amyloid fibrils. Increasing evidence suggests that soluble, low molecular weight aggregates play a key role in disease-associated toxicity. Within these aggregates, protofibrillar loop-like structures have been observed for a variety of amyloid systems and their presence in brain tissues is associated with high levels of neuropathology. However, their mechanism of formation and relationship with mature fibrils has largely remained challenging to elucidate. Here, we use atomic force microscopy and statistical theory of biopolymers to characterise amyloid ring structures derived from the brains of AD patients. We analyse the bending fluctuations of protofibrils and show that the process of loop formation is governed by the mechanical properties of their chains. We conclude that ex vivo protofibril chains possess greater flexibility than that imparted by hydrogen-bonded networks characteristic of mature amyloid fibrils, such that they are able to form end-to-end connections. Furthermore, we show that these findings can be extended to several amyloid systems, giving a general framework relating the mechanical properties of assemblies and the conditions in which they can form loop structures. These results explain the diversity in the structures formed from protein aggregation and sheds light on the links between early forms of flexible ring-forming aggregates and their role in disease.

Carbon nanotube (CNT)-copper nanocomposites are promising materials for light-weight high-ampacity conductors. The key issue in hybridization of CNT and metal is creating a strong bonding between them. This requires proper modification of the CNT surface. However, experimental works on determining the effect of interfacial functionalization on the properties of the metal/CNT system is scarce. In this paper, the effect of CNT surface modification on the morphology, interfacial interactions, and electrical properties Cu/CNT hybrid system is investigated. For this purpose, CNTs with carboxyl, thiol, and nitrogen doped surface groups were used as substrate for growth of Cu particles via a facile electrochemical process. It is observed that not only the morphology but also the chemical state of the Cu deposits are affected by the surface functional group on CNT. Thiol group significantly enhances copper wettability towards CNT, facilitating a uniform deposition of copper, and impedes oxidation. Also, Cu/CNT thin films fabricated via vacuum filtration that contain thiol-activated CNTs shows four and seven times higher electrical conductivity compared with systems that contain carboxyl and N-doped surface groups, respectively.

Abstract Solution processing of metal oxide-based semiconductors is an attractive route for low-cost fabrication of thin films devices. ZnO thin films were synthesized from one-step spin coating-pyrolysis technique using zinc neodecanoate precursor. X-ray diffraction (XRD), UV–visible optical transmission spectrometry and photoluminescence spectroscopy suggested conversion to polycrystalline ZnO phase for decomposition temperatures higher than 400 °C. A 15 % precursor concentration was found to produce optimal TFT performance on annealing at 500 °C, due to generation of sufficient charge percolation pathways. The device performance was found to improve upon increasing the annealing temperature and the optimal saturation mobility of 0.1 cm2 V−1 s−1 with ION/IOFF ratio ~ 107 was achieved at 700 °C annealing temperature. The analysis of experimental results based on theoretical models to understand charge transport envisaged that the grain boundary depletion region is major source of deep level traps and their effective removal at increased annealing temperature leads to evolution of transistor performance. Graphic Abstract Single-step spin coating-pyrolysis synthesis of ZnO thin films from non-aqueous precursor zinc neodecanoate has been investigated for transistor applications.

There is growing demand for lightweight flexible supercapacitors with high electrochemical performance for wearable and portable electronics. Here, we spun nanoparticles of nickel–manganese oxides along with carbon nanotubes into carbon nanofibers and engineered a 3D networked Ni–Mn oxides/CNT@CNF free-standing membrane for flexible supercapacitor applications. The electrospinning process controlled the nanoparticle aggregation while subsequent heat treatment generates nanochannels in the fibres, resulting in a very porous tubular nanocomposite structure. The preparation process also enabled good interfacial contact between the nanoparticles and the conductive carbon network. The resulting Ni–Mn oxides/CNT@CNF membrane displays high mass loading (Ni–Mn oxides) of 855 mg cm−3 and low CNT incorporation of ∼0.4%. The outstanding porous structure, synergy of the carbon with Ni–Mn oxides, and fast and facile faradaic reactions on the electrode were responsible for the superior volumetric capacitance of 250 F cm−3 at 1 A cm−3, energy density as high as 22 mW h cm−3 and an excellent power density of 12 W cm−3. Despite the low CNT loading, the hybrid electrode exhibits excellent cycling performance with capacitance retention of 96.4% after 10 000 cycles evidencing a well-preserved Ni–manganese oxide nanostructure throughout the cycling. The resulting outstanding electrochemical performances of the Ni–Mn oxides/CNT@CNF synergic system offer new insights into effective utilization of transition metal oxides for establishing high-performance flexible supercapacitors within a confined volume.

© 2019 Farjadian et al. Background: Smart materials capable of responding to external stimuli are noteworthy candidates in designing drug delivery systems. In many of the recent research, temperature and pH have been recognized as the main stimulating factors in designing systems for anticancer drugs delivery systems. Purpose: In this study, thermo and pH-responsive character of a nano-carrier drug delivery platform based on lysine modified poly (vinylcaprolactam) hydrogel conjugated with doxorubicin was assessed. Methods: Poly (vinylcaprolactam) cross-linked with poly (ethyleneglycol) diacrylate was prepared via RAFT polymerization, and the prepared structure was linked with lysine through ring-opening. The anti-cancer drug doxorubicin, was linked to lysine moiety of the prepared structure via Schiff-base reaction. The prepared platform was characterized by 1HNMR and FTIR, while molecular weight characterization was performed by size exclusion chromatography. The temperature-responsive activity was evaluated using differential scanning calorimetry and dynamic light scattering. In vitro release pattern in simulated physiologic pH at 37°C was compared with acidic pH attributed to tumor site and elevated temperature. The anticancer efficiency of the drug-conjugated structure was evaluated in breast cancer cell line MCF-7 in 24 and 48 h, and cell uptake assay was performed on the same cell line. Conclusion: According to the results, well-structure defined smart pH and temperature responsive nano-hydrogel was prepared. The enhanced release rates are observed at acidic pH and elevated temperature. We have concluded that the doxorubicin-conjugated nanoparticle results in higher cellular uptakes and more cytotoxicity.

Single-molecule imaging of proteins using atomic force microscopy (AFM) is crucially dependent on protein attachment to ultraflat substrates. The template-stripping (TS) technique, which can be used to create large areas of atomically flat gold, has been used to great effect for this purpose. However, this approach requires an epoxy, which can swell in solution, causing surface roughening and substantially increasing the thickness of any sample, preventing its use on acoustic resonators in liquid. Diffusion bonding techniques should circumvent this problem but cannot be used on samples containing patterned features with mismatched heights because of cracking and poor transfer. Here, we describe a new technique called pressure-forming TS (PTS), which permits an ultraflat (0.35 ± 0.05 nm root-mean-square roughness) layer of gold to be transferred to the surface of a patterned substrate at low temperature and pressure. We demonstrate this technique by modifying a quartz crystal microbalance (QCM) sensor to contain an ultraflat gold surface. Standard QCM chips have substantial roughness, preventing AFM imaging of proteins on the surface after measurement. With our approach, there is no need to run samples in parallel: the modified QCM chip is flat enough to permit high-contrast AFM imaging after adsorption studies have been conducted. The PTS-QCM chips are then used to demonstrate adsorption of bovine serum albumin in comparison to rough QCM chips. The ability to attach thin layers of ultraflat metals to surfaces of heterogeneous nature without epoxy will have many applications in diverse fields where there is a requirement to observe nanoscale phenomena with multiple techniques, including surface and interfacial science, optics, and biosensing.

Every biosensor, bioengineered scaffold or biomedical implant depends crucially on an ability to control protein adsorption at the material surface. Yet the adsorption of proteins to solid surfaces in aqueous media is a complex and poorly understood phenomenon. To gain further insights we study protein adsorption using the quartz crystal microbalance for 10 model globular proteins interacting with positive, negative, neutral, hydrophobic and mixed alkanethiol monolayers as well as silica, polystyrene and Teflon, equating to approximately 200 protein-surface combinations. The charge state of the materials in liquid was measured with atomic force microscopy using a colloidal probe and numerically solving the full non-linear Poisson-Boltzmann equation. This approach has allowed us to address some of the important questions surrounding the basic principles that govern protein adsorption including the relative importance of net charge and hydrophobicity and why some materials are protein resistant. With our set of mixed monolayer surfaces, we can modulate charge over a wide range whilst eliminating hydrophobic interactions and vice versa- thus permitting determination of the functional dependence of adsorption on these parameters. This has led us to develop two empirical predictive models with up to 90% accuracy that together encompass most materials relevant to biotechnological and biomedical applications.

This Research Article discusses the growth of polycrystalline, self-supporting ZnO nanofibers, which can detect nitrogen dioxide (NO2) gas down to 1 part per billion (ppb), one of the smallest detection limits reported for NO2 using ZnO. A new and innovative method has been developed for growing polycrystalline ZnO nanofibers. These nanofibers have been created using core-shell electrospinning of inorganic metal precursor zinc neodecanoate, where growth occurs at the core of the nanofibers. This process produces contamination-free, self-supporting, polycrystalline ZnO nanofibers of an average diameter and grain size 50 and 8 nm, respectively, which are ideal for gas sensing applications. This process opens up an exciting opportunity for creating nanofibers from a variety of metal oxides, facilitating many new applications especially in the areas of sensors and wearable technologies.

Zinc oxide (ZnO) has been extensively investigated for use in large-area electronics; in particular, the solution-processing routes have shown increasing promise towards low-cost fabrication. However, top-down fabrication approaches with nanoscale resolution, towards aggressively scaled device platforms, are still underexplored. This study reports a novel approach of direct-write electron-beam lithography (DW-EBL) of solution precursors as negative tone resists, followed by optimal precursor processing to fabricate micron/nano-field-effect transistors (FETs). It is demonstrated that the mobility and current density of ZnO FETs can be increased by two orders of magnitude as the precursor pattern width is decreased from 50 µm to 100 nm. These nano-FET devices exhibit field-effect mobility exceeding ≈30 cm2 V−1 s−1 and on-state current densities reaching 10 A m−1, the highest reported so far for direct-write precursor-patterned nanoscale ZnO FETs. Using atomic force microscopy and parametric modeling, the origin of such device performance improvement is investigated. The findings emphasize the influence of pre-decomposition nanoscale precursor patterning on the grain morphology evolution in ZnO and, consequently, open up large-scale integration, and miniaturization opportunities for solution-processed, high-performance nanoscale oxide FETs.

Carbon nanotubes and copper composites have long been predicted as new conductors that may benefit from the high conductivity of copper and the lightweight and very high ampacity of carbon nanotubes. One of the key challenges has been to integrate Cu with CNTs and form a free-standing composite wire. We have achieved this by first making a CNTs filament using high concentration (20 g L-1) CNTs dispersion, an acid-free wet spinning process and then by replacing the polymer with copper using heat based polymer decomposition and periodic pulse reverse electroplating. It has been demonstrated that indeed the specific conductivity and the current-carrying capability (or ampacity) are increased manifold. MWCNTs/Cu composite wires developed in this paper have electrical conductivity σ ~ 5.5 ×105 S cm-1. These MWCNTs/Cu wires are 2/3rd the weight of bulk Cu wires. Their specific electrical conductivity is σρ~ 9.38 ×104 S cm2 g-1 which is 45 % higher than International Annealed Copper Standard (IACS) Cu. These composite wires have an ampacity of A~ 20 ×105 A cm-2 and 4×105 A cm-2 for 1.5 mm and 17 mm gauge length wires respectively, which is 4 to 6 times higher than pure Cu depending on the wire lengths. MWCNTs volume percentage in the MWCNTs/Cu wire is about 40%.

Colloidal quantum dots (QDs) have unique optical and electrical properties with promising applications in next‐generation semiconductor technologies, including displays, lighting, solar cells, photodetectors, and image sensors. Advanced analytical tools to probe the optical, morphological, structural, compositional, and electrical properties of QDs and their ensemble solid films are of paramount importance for the understanding of their device performance. In this review, comprehensive studies on the state‐of‐the‐art metrology approaches used in QD research are introduced, with particular focus on time‐resolved (TR) and spatially resolved (SR) spectroscopy and microscopy. Through discussing these analysis techniques in different QD system, such as various compositions, sizes, and shell structures, the critical roles of these TR‐spectroscopic and SR‐microscopic techniques are highlighted, which provide the structural, morphological, compositional, optical, and electrical information to precisely design QDs and QD solid films. The employment of TR and SR analysis in integrated QD device systems is also discussed, which can offer detailed microstructural information for achieving high performance in specific applications. In the end, the current limitations of these analytical tools are discussed, and the future development of the possibility of interdisciplinary research in both QD fundamental and applied fields is prospected.

An increasing number of technologies require the fabrication of micro- and nanostructures over large areas. Soft lithographic methods are gaining in popularity for the manufacture of low-cost micrometre and sub-micrometre structures. Increasingly, these methods developed to structure organic resists can also be used to pattern inorganic materials. Here we introduce a simple lithographic technique that is able to pattern ceramic TiO micro- and nanostructures with high fidelity. Our method makes use of an electrohydrodynamic (EHD) film instability that is controlled by a laterally modulated electric field. A spin-coated film of a stabilized metal alkoxide precursor material was patterned using EHD lithography followed by a heat treatment at 400 °C to yield crystalline TiO micropatterns. Our technique is rather general and can be extended to a number of single- and multicomponent oxide systems.

Carbon electronics is a growing field that spans printable electronics, energy storage devices, and bio-sensors. The commercialization of these carbon-based technologies requires a scalable production of high conductivity, acid-free carbon nanotube ink dispersions. Super acids have been used to achieve high concentration CNT inks however a scalable acid-free process to achieve similar concentrations has been missing for a long time. In this work, we demonstrate that water and sodium-cellulose are sufficient for achieving a scalable production of highly conductive CNT based ink, provided the solution is processed through a very high shear microfluidizer. Materials used in this process are acid-free and require no post-processing, such as centrifuging or heating. We have achieved conductivity and sheet resistance of 3.6±0.2x105 S.m-1 and 0.11 Ω.□-1mil-1 respectively, which are among the best-reported values for any un-doped carbon-based film. The thermal conductivity of the free-standing carbon films is 43±4 W m-1K-1. Using this method uniformly dispersed CNT inks, of viscosity >1Pa-s, are produced. Once printed on paper, these CNT films show pronounced resilience to mechanical deformation. This simple but scalable process provides a viable technology for using carbon-based conducting inks for printing large-scale devices.

Graphical abstract, Mycobacterium tuberculosis (Mtb) remains a major challenge to global health, made worse by the spread of multi-drug resistance. Currently, the efficacy and safety of treatment is limited by difficulties in achieving and sustaining adequate tissue antibiotic concentrations while limiting systemic drug exposure to tolerable levels. Here we show that nanoparticles generated from a polymer-antibiotic conjugate (‘nanobiotics’) deliver sustained release of active drug upon hydrolysis in acidic environments, found within Mtb-infected macrophages and granulomas, and can, by encapsulation of a second antibiotic, provide a mechanism of synchronous drug delivery. Nanobiotics are avidly taken up by infected macrophages, enhance killing of intracellular Mtb, and are efficiently delivered to granulomas and extracellular mycobacterial cords in vivo in an infected zebrafish model. We demonstrate that isoniazid (INH)-derived nanobiotics, alone or with additional encapsulation of clofazimine (CFZ), enhance killing of mycobacteria in vitro and in infected zebrafish, supporting the use of nanobiotics for Mtb therapy and indicating that nanoparticles generated from polymer-small molecule conjugates might provide a more general solution to delivering co-ordinated combination chemotherapy.

The use of peptides as therapeutic agents is undergoing a renaissance with the expectation of new drugs with enhanced levels of efficacy and safety. Their clinical potential will be only fully realised once their physicochemical and pharmacokinetic properties have been precisely controlled. Here we demonstrate a reversible peptide self-assembly strategy to control and prolong the bioactivity of a native peptide hormone in vivo. We show that oxyntomodulin, a peptide with potential to treat obesity and diabetes, self-assembles into a stable nanofibril formulation which subsequently dissociates to release active peptide and produces a pharmacological effect in vivo. The subcutaneous administration of the nanofibrils in rats results in greatly prolonged exposure, with a constant oxyntomodulin bioactivity detectable in serum for at least 5 days as compared to free oxyntomodulin which is undetectable after only 4 h. Such an approach is simple, cost-efficient and generic in addressing the limitations of peptide therapeutics., The clinical potential of peptide therapeutic agents can only be fully realised once their physicochemical and pharmacokinetic properties are precisely controlled. Here the authors show a reversible peptide self-assembly strategy to control and prolong the bioactivity of a native peptide hormone in vivo.

The human peptide hormone Oxyntomodulin (Oxm) is known to induce satiety, increase energy expenditure, and control blood glucose in humans, making it a promising candidate for treatment of obesity and/or type 2 diabetes mellitus. However, a pharmaceutical exploitation has thus far been impeded by fast in vivo clearance and the molecule‘s sensitivity to half-life extending structural modifications. We recently showed that Oxm self-assembles into amyloid-like nanofibrils that continuously release active, soluble Oxm in a peptide-deprived environment. S.c. injected Oxm nanofibrils extended plasma exposure from a few hours to five days in rodents, compared to s.c. applied soluble Oxm. Here we show that Oxm fibril elongation kinetics and thermodynamics display a uniquely low temperature optimum compared to previously reported amyloid-like peptide and protein assemblies. Elongation rate is optimal at room temperature, with association rates 2–3 times higher at 25 °C than at ≥37 °C or ≤20 °C. We deduce from a combination of Cryo electron microscopy and spectroscopic methods that Oxm fibrils have a double-layered, triangular cross-section composed of arch-shaped monomers. We suggest a thermodynamic model that links the necessary molecular rearrangements during fibrillation and peptide release to the unique temperature effects in Oxm self-assembly and disassembly.

Background Smart materials capable of responding to external stimuli are noteworthy candidates in designing drug delivery systems. In many of the recent research, temperature and pH have been recognized as the main stimulating factors in designing systems for anti-cancer drugs delivery systems. Purpose In this study, thermo and pH-responsive character of a nano-carrier drug delivery platform based on lysine modified poly (vinylcaprolactam) hydrogel conjugated with doxorubicin was assessed. Methods Poly (vinylcaprolactam) cross-linked with poly (ethyleneglycol) diacrylate was prepared via RAFT polymerization, and the prepared structure was linked with lysine through ring-opening. The anti-cancer drug doxorubicin, was linked to lysine moiety of the prepared structure via Schiff-base reaction. The prepared platform was characterized by 1HNMR and FT-IR, while molecular weight characterization was performed by size exclusion chromatography. The temperature-responsive activity was evaluated using differential scanning calorimetry and dynamic light scattering. In vitro release pattern in simulated physiologic pH at 37°C was compared with acidic pH attributed to tumor site and elevated temperature. The anticancer efficiency of the drug-conjugated structure was evaluated in breast cancer cell line MCF-7 in 24 and 48 h, and cell uptake assay was performed on the same cell line. Conclusion According to the results, well-structure defined smart pH and temperature responsive nano-hydrogel was prepared. The enhanced release rates are observed at acidic pH and elevated temperature. We have concluded that the doxorubicin-conjugated nanoparticle results in higher cellular uptakes and more cytotoxicity.

Metal oxides are promising materials for supercapacitors due to their high theoretical capacitance. However, their poor electrical conductivity is a major challenge. Hybridization with conductive nanostructured carbon-based materials such as carbon nanotubes (CNTs) has been proposed to improve the conductivity and increase the surface area. In this work, CNTs are used as a template for synthesizing porous thin films of SnO2-CuO-Cu2O (SnO2-Cu x O) via an electroless deposition technique. Tin, with its high wettability and electrical conductivity, acts as an intermediate layer between copper and the CNTs and provides a strong interaction between them. We also observed that by controlling the interfacial characteristics of CNTs and varying the composition of the electroless bath, the SnO2-Cu x O thin film morphology can be easily manipulated. Electrochemical characterizations show that CNT/SnO2-Cu x O nanocomposite possesses pseudocapacitive behavior that reaches a specific capacitance of 662 F g-1 and the retention is 94% after 5000 cycles, which outperforms any known copper and tin-based supercapacitors in the literature. This excellent performance is mainly attributed to high specific surface area, small particle size, the synergistic effect of Sn, and conductivity improvement by using CNTs. The combination of CNTs and metal oxides holds promise for supercapacitors with improved performance.

This Research Article discusses the growth of polycrystalline, self-supporting ZnO nanofibers, which can detect nitrogen dioxide (NO

We demonstrate the interplay between surface recombination dynamics and environmental temperature in UV photoresponse of ZnO nanowire field effect transistors (FETs) with and without a passivation layer. We find that optoelectronic performance and photoresponse mechanism can be significantly altered by temperature, influencing surface chemical interaction and reaction associated with charge trapping. Particularly, regardless of surface passivation on nanowires, photocurrent gains and decay rate are drastically enhanced with increasing temperature. Furthermore, the temperature dependence of photoresponse behavior in nanowire FETs is discussed in terms of surface recombination rates, carrier concentration, surface potential barrier height, and charge trapping rates on the surface.

This paper addresses the synthesis and a detailed electrical analysis of individual copper nanowires (CuNWs). One dimensional CuNWs are chemically grown using Bromide ions (Br-) as a co-capping agent. By partially replacing alkyl amines with Br-, the isotropic growth on Cu seeds was suppressed during the synthesis. To study the electrical properties of individual CuNWs, a fabrication method is developed which does not require any e-beam lithography process. Chemically grown CuNWs have an ampacity of about 30 million amps per cm2, which is more than one order of magnitude larger than the bulk Cu. These good qualities easy to synthesize CuNWs are an excellent candidate for creating high ampacity wires and flexible printable electronics.

We demonstrate the current-dependent consecutive appearance of two different negative differential resistance (NDR) transitions in a single crystalline VO

Diverse functionalities of liquid crystals (LCs) offer enormous opportunities for their potential use in advanced mobile and smart displays, as well as novel non-display applications. Here, we present snapshots of the research carried out on emerging applications of LCs ranging from electronics to holography and self-powered systems. In addition, we will show our recent results focused on the development of new LC applications, such as programmable transistors, a transparent and active-type two-dimensional optical array and self-powered display systems based on LCs, and will briefly discuss their novel concepts and basic operating principles. Our research will give insights not only into comprehensively understanding technical and scientific applications of LCs, but also developing new discoveries of other LC-based devices. © 2014 by the authors.

Glioblastoma multiforme (GBM) remains the most aggressive and challenging brain tumour to treat. We report the first successful chemo-radiotherapy on patient derived treatment resistant GBM cells using a cisplatin-tethered gold nanosphere. After intracellular uptake, the nanosphere effects DNA damage which initiates caspase-mediated apoptosis in those cells. In the presence of radiation, both gold and platinum of cisplatin, serve as high atomic number radiosensitizers leading to the emission of ionizing photoelectrons and Auger electrons. This resulted in enhanced synergy between cisplatin and radiotherapy mediated cytotoxicity, and photo/Auger electron mediated radiosensitisation leading to complete ablation of the tumour cells in an in vitro model system. This study demonstrates the potential of designed nanoparticles to target aggressive cancers in the patient derived cell lines providing a platform to move towards treatment strategies.

Nucleoside diphosphate kinases (NDPKs) are crucial elements in a wide array of cellular physiological or pathophysiological processes such as apoptosis, proliferation, or metastasis formation. Among the NDPK isoenzymes, NDPK-B, a cytoplasmic protein, was reported to be associated with several biological membranes such as plasma or endoplasmic reticulum membranes. Using several membrane models (liposomes, lipid monolayers, and supported lipid bilayers) associated with biophysical approaches, we show that lipid membrane binding occurs in a two-step process: first, initiation by a strong electrostatic adsorption process and followed by shallow penetration of the protein within the membrane. The NDPK-B binding leads to a decrease in membrane fluidity and formation of protein patches. The ability of NDPK-B to form microdomains at the membrane level may be related to protein-protein interactions triggered by its association with anionic phospholipids. Such accumulation of NDPK-B would amplify its effects in functional platform formation and protein recruitment at the membrane.

The construction of protein-based photoelectrochemical cells that produce a variety of alternating currents in response to discontinuous illumination is reported. The photovoltaic component is a protein complex from the purple photosynthetic bacterium Rhodobacter sphaeroides which catalyses photochemical charge separation with a high quantum yield. Photoelectrochemical cells formed from this protein, a mobile redox mediator and a counter electrode formed from cobalt disilicide, titanium nitride, platinum, or multi-walled carbon nanotubes (MWCNT) generate a direct current during continuous illumination and an alternating current with different characteristics during discontinuous illumination. In particular, the use of superhydrophobic MWCNT as the back electrode results in a near symmetrical forward and reverse current upon light on and light off, respectively. The symmetry of the AC output of these cells is correlated with the wettability of the counter electrode. Potential applications of a hybrid biological/synthetic solar cell capable of generating an approximately symmetrical alternating current are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Electrostatic forces play a key role in mediating interactions between proteins. However, gaining quantitative insights into the complex effects of electrostatics on protein behavior has proved challenging, due to the wide palette of scenarios through which both cations and anions can interact with polypeptide molecules in a specific manner or can result in screening in solution. In this article, we have used a variety of biophysical methods to probe the steady-state kinetics of fibrillar protein self-assembly in a highly quantitative manner to detect how it is modulated by changes in solution ionic strength. Due to the exponential modulation of the reaction rate by electrostatic forces, this reaction represents an exquisitely sensitive probe of these effects in protein-protein interactions. Our approach, which involves a combination of experimental kinetic measurements and theoretical analysis, reveals a hierarchy of electrostatic effects that control protein aggregation. Furthermore, our results provide a highly sensitive method for the estimation of the magnitude of binding of a variety of ions to protein molecules.

The role of the collagen-platelet interaction is of crucial importance to the haemostatic response during both injury and pathogenesis of the blood vessel wall. Of particular interest is the high affinity interaction of the platelet transmembrane receptor, alpha 2 beta 1, responsible for firm attachment of platelets to collagen at and around injury sites. We employ single molecule force spectroscopy (SMFS) using the atomic force microscope (AFM) to study the interaction of the I-domain from integrin alpha 2 beta 1 with a synthetic collagen related triple-helical peptide containing the high-affinity integrin-binding GFOGER motif, and a control peptide lacking this sequence, referred to as GPP. By utilising synthetic peptides in this manner we are able to study at the molecular level subtleties that would otherwise be lost when considering cell-to-collagen matrix interactions using ensemble techniques. We demonstrate for the first time the complexity of this interaction as illustrated by the complex multi-peaked force spectra and confirm specificity using control blocking experiments. In addition we observe specific interaction of the GPP peptide sequence with the I-domain. We propose a model to explain these observations.

Single molecule force spectroscopy is a technique that can be used to probe the interaction force between individual biomolecular species. We focus our attention on the tip and sample coupling chemistry, which is crucial to these experiments. We utilised a novel approach of mixed self-assembled monolayers of alkanethiols in conjunction with a heterobifunctional crosslinker. The effectiveness of the protocol is demonstrated by probing the biotin-avidin interaction. We measured unbinding forces comparable to previously reported values measured at similar loading rates. Specificity tests also demonstrated a significant decrease in recognition after blocking with free avidin.

The innately highly efficient light-powered separation of charge that underpins natural photosynthesis can be exploited for applications in photoelectrochemistry by coupling nanoscale protein photoreaction centers to man-made electrodes. Planar photoelectrochemical cells employing purple bacterial reaction centers have been constructed that produce a direct current under continuous illumination and an alternating current in response to discontinuous illumination. The present work explored the basis of the open-circuit voltage (V(OC)) produced by such cells with reaction center/antenna (RC-LH1) proteins as the photovoltaic component. It was established that an up to ~30-fold increase in V(OC) could be achieved by simple manipulation of the electrolyte connecting the protein to the counter electrode, with an approximately linear relationship being observed between the vacuum potential of the electrolyte and the resulting V(OC). We conclude that the V(OC) of such a cell is dependent on the potential difference between the electrolyte and the photo-oxidized bacteriochlorophylls in the reaction center. The steady-state short-circuit current (J(SC)) obtained under continuous illumination also varied with different electrolytes by a factor of ~6-fold. The findings demonstrate a simple way to boost the voltage output of such protein-based cells into the hundreds of millivolts range typical of dye-sensitized and polymer-blend solar cells, while maintaining or improving the J(SC). Possible strategies for further increasing the V(OC) of such protein-based photoelectrochemical cells through protein engineering are discussed.

We report a hydrothermal synthesis method for MgO shell coatings directly onto the surface of ZnO nanowire arrays. The entire process can be carried out below 100 °C. The MgO shells are produced by the addition of 10 mM magnesium nitrate with 0.2 M sodium hydroxide in water, resulting in a shell thickness of up to 8 nm, verified by high resolution transmission electron microscopy. The viability of the MgO layer as a functional element of optoelectronic devices was tested on solid-state organic hole-transporter based dye-sensitized solar cells. Incorporation of the MgO shell into the solar cell resulted in substantive efficiency improvements of over 400% in comparison to the pristine ZnO nanowire based photovoltaics, indicating that electrons can efficiently tunnel through the 'insulating' MgO shell.

We carried out temperature-dependent photoluminescence measurements to investigate the influence of surface roughness on the phonon-assisted emission of the surface-tailored ZnO nanowires (NWs). For the rough ZnO NWs, the observation of strong defect emission with vibration peaks by the exciton-phonon coupling reflects the presence of a high density of surface defects, resulting in a rapid shift to lower energy region of free exciton emission and a strong contribution of the first order phonon-assisted free exciton in ultraviolet emission. This investigation indicates that the surface defects associated with roughness have a significant influence on the phonon-assisted exciton emission. © 2009 American Institute of Physics.

We demonstrate modulations of electrical conductance and hysteresis behavior in ZnO nanowire transistors via electrically polarized switching of ferroelectric liquid crystal (FLC). After coating a nanowire channel in the transistors with FLCs, we observed large increases in channel conductance and hysteresis width, and a strong dependence of hysteresis loops on the polarization states associated with the orientation of electric dipole moments along the direction of the gate electric field. Furthermore, the reversible switching and retention characteristics provide the feasibility of creating a hybrid system with switch and memory functions. © 2013 American Institute of Physics.

A new layout of predictable and controllable complementary logic circuits based on hybrid nanodevices comprising p-channel single-walled carbon nanotube (SWNT) and n-channel zinc oxide (ZnO) nanowire transistors providing a hybrid approach to combine advantageous characteristic functions for the modulation of the current and operating voltage in transistors through proton radiation generated charge, was studied. A suspension of SWNTs obtained through an arc discharge process in 1,2, dichlorobenzene (o-DCB) was prepared by a combination of sonication and centrifugation. 1 mg of SWNTs in 10 mL of o-DCB was sonicated for 5 mm and the SWNT suspension was then centrifuged for 200 mm at 16000 g followed by ultra centrifugation for 2 h at 325 000 g. The current-VTCs of transistors and logic circuits were measured using a semiconductor parameter analyzer. It was possible to achieve high performance logic circuits by selectively controlling the threshold voltages of transistors through the population of proton radiation generated charges in the dielectric layer.

We study two distinctly ordered condensed phases of polypeptide molecules, amyloid fibrils and amyloidlike microcrystals, and the first-order twisting phase transition between these two states. We derive a single free-energy form which connects both phases. Our model identifies relevant degrees of freedom for describing the collective behavior of supramolecular polypeptide structures, reproduces accurately the results from molecular dynamics simulations as well as from experiments, and sheds light on the uniform nature of the dimensions of different peptide fibrils. © 2012 American Physical Society.

We have applied a MgO and a ZrO2 shell deposition method to control the interface between two indolenebased organic dyes in solid-state dye-sensitized solar cells. The shell deposition was carried out at less than 100 °C, and shell thickness was shown to be 2 nm for the ZrO2 and 6-10 nm for the MgO by transmission electron microscopy. X-ray photoelectron spectroscopy has shown the initial ZnO NWs and core-shell structures have little surface water contamination. The use of suitable dyes, D102 and D149, has led to power conversion efficiency for ZnO NW based hybrid solar cells of 0.71%. Transient absorption measurements indicate that enhancements in photoinduced charge generation with core-shell formation are the main factor leading to the improved device efficiency. © 2009 American Chemical Society.

We investigated the UV photoconductivity characteristics of ZnO nanowire field effect transistors (FETs) irradiated by proton beams. After proton beam irradiation (using a beam energy of 10 MeV and a fluence of 1012 cm− 2), the drain current and carrier density in the ZnO nanowire FETs decreased, and the threshold voltage shifted to the positive gate bias direction due to the creation of interface traps at the SiO2/ZnO nanowire interface by the proton beam. The interface traps produced a higher surface barrier potential and a larger depletion region at the ZnO nanowire surface, affecting the photoconductivity and its decay time. The UV photoconductivity of the proton-irradiated ZnO nanowire FETs was higher and more prolonged than that of the pristine ZnO nanowire FETs. The results extend our understanding of the UV photoconductivity characteristics of ZnO nanowire devices and other materials when irradiated with highly energetic particles.

The molecular chaperone αB-crystallin is a small heat-shock protein that is upregulated in response to a multitude of stress stimuli, and is found colocalized with Aβ amyloid fibrils in the extracellular plaques that are characteristic of Alzheimer's disease. We investigated whether this archetypical small heat-shock protein has the ability to interact with Aβ fibrils in vitro. We find that αB-crystallin binds to wild-type Aβ42 fibrils with micromolar affinity, and also binds to fibrils formed from the E22G Arctic mutation of Aβ42. Immunoelectron microscopy confirms that binding occurs along the entire length and ends of the fibrils. Investigations into the effect of αB-crystallin on the seeded growth of Aβ fibrils, both in solution and on the surface of a quartz crystal microbalance biosensor, reveal that the binding of αB-crystallin to seed fibrils strongly inhibits their elongation. Because the lag phase in sigmoidal fibril assembly kinetics is dominated by elongation and fragmentation rates, the chaperone mechanism identified here represents a highly effective means to inhibit fibril proliferation. Together with previous observations of αB-crystallin interaction with α-synuclein and insulin fibrils, the results suggest that this mechanism is a generic means of providing molecular chaperone protection against amyloid fibril formation.

We demonstrated the nonvolatile memory functionality of ZnO nanowire field effect transistors (FETs) using mobile protons that are generated by high-pressure hydrogen annealing (HPHA) at relatively low temperature (400 °C). These ZnO nanowire devices exhibited reproducible hysteresis, reversible switching, and nonvolatile memory behaviors in comparison with those of the conventional FET devices. We show that the memory characteristics are attributed to the movement of protons between the Si/SiO(2) interface and the SiO(2)/ZnO nanowire interface by the applied gate electric field. The memory mechanism is explained in terms of the tuning of interface properties, such as effective electric field, surface charge density, and surface barrier potential due to the movement of protons in the SiO(2) layer, consistent with the UV photoresponse characteristics of nanowire memory devices. Our study will further provide a useful route of creating memory functionality and incorporating proton-based storage elements onto a modified CMOS platform for FET memory devices using nanomaterials.

5 páginas, 5 figuras.-- et al., A novel all-inorganic electroluminescent device is demonstrated based on highly luminescent CdTe nanocrystals intercalated within a laminar hydrotalcite-like structure. The laminar scaffold acts to both support and distribute the CdTe nanocrystals. The device is synthesized using simple wet chemical processes at room temperature in ambient conditions. It has high thermal stability, operating continuously up to 90 °C, and a maximum efficiency at J = 0.12 A cm−2. The device is targeted at the automotive industry., The authors acknowledge funding from the EU FP6 project “Stabilight” (Grant No. 017328).

The fabrication of very narrow metal lines by the lift-off technique, especially below sub-10 nm, is challenging due to thinner resist requirements in order to achieve the lithographic resolution. At such small length scales, when the grain size becomes comparable with the line-width, the built-in stress in the metal film can cause a break to occur at a grain boundary. Moreover, the line-width roughness (LWR) from the patterned resist can result in deposited metal lines with a very high LWR, leading to an adverse change in device characteristics. Here a new approach that is not based on the lift-off technique but rather on low temperature hydrogen reduction ofelectron-beam patterned metal naphthenates is demonstrated. This not only enables the fabrication of sub-10 nm metal lines of good integrity, but also of low LWR, below the limit of 3.2 nm discussed in the International Technology Roadmap for Semiconductors. Using this method, sub-10 nm nickel wires are obtained by reducing patterned nickel naphthenate lines in a hydrogen-rich atmosphere at 500°C for 1 h. The LWR (i.e., 3 σ LWR ) of these nickel nanolines was found to be 2.9 nm. The technique is general and is likely to be suitable for fabrication of nanostructures of most commonly used metals (and their alloys), such as iron, cobalt, nickel, copper, tungsten, molybdenum, and so on, from their respective metal―organic compounds.

We present a material assembly route for the manufacture of dye-sensitized solar cells, coupling a high-surface mesoporous layer to a three-dimensional photonic crystal (PC). Material synthesis aided by self-assembly on two length scales provided electrical and pore connectivity at the mesoporous and the microporous level. This construct allows effective dye sensitization, electrolyte infiltration, and charge collection from both the mesoporous and the PC layers, opening up additional parameter space for effective light management by harvesting PC-induced resonances.

The physicochemical parameters of biomolecules are the key determinants of the multitude of processes that govern the normal and aberrant behavior of living systems. A particularly important aspect of such behavior is the role it plays in the self-association of proteins to form organized aggregates such as the amyloid or amyloid-like fibrils that are associated with pathological conditions including Alzheimer's disease and Type II diabetes. In this study we describe quantitative quartz crystal microbalance measurements of the kinetics of the growth of amyloid fibrils in a range of crowded environments and in conjunction with theoretical predictions demonstrate the existence of general relationships that link the propensities of protein molecules to aggregate with fundamental parameters that describe their specific structures and local environments.