Origin of Polarization in Bismuth Sodium Titanate-Based Ceramics.

The classical view of the structural changes that occur at the ferroelectric transition in perovskite-structured systems, such as BaTiO3, is that polarization occurs due to the off-center displacement of the B-site cations. Here, we show that in the bismuth sodium titanate (BNT)-based composition 0.2(Ba0.4Sr0.6TiO3)-0.8(Bi0.5Na0.5TiO3), this model does not accurately describe the structural situation. Such BNT-based systems are of interest as lead-free alternatives to currently used materials in a variety of piezo-/ferroelectric applications. A combination of high-resolution powder neutron diffraction, impedance spectroscopy, and ab initio calculations reveals that Ti4+ contributes less than a third in magnitude to the overall polarization and that the displacements of the O2- ions and the A-site cations, particularly Bi3+, are very significant. The detailed examination of the ferroelectric transition in this system offers insights applicable to the understanding of such transitions in other ferroelectric perovskites, particularly those containing lone pair elements.

Interplay between Side Chain Density and Polymer Alignment: Two Competing Strategies for Enhancing the Thermoelectric Performance of P3HT Analogues.

A series of polythiophenes with varying side chain density was synthesized, and their electrical and thermoelectric properties were investigated. Aligned and non-aligned thin films of the polymers were characterized in the neutral and chemically doped states. Optical and diffraction measurements revealed an overall lower order in the thin films with lower side chain density, also confirmed using polarized optical experiments on aligned thin films. However, upon doping the non-aligned films, a sixfold increase in electrical conductivity was observed for the polythiophene with the lowest side chain density compared to poly(3-hexylthiophene) (P3HT). We found that the improvement in conductivity was not due to a larger charge carrier density but an increase in charge carrier mobility after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). On the other hand, doped aligned films did not show the same trend; lower side chain density instead led to a lower conductivity and Seebeck coefficient compared to those for P3HT. This was attributed to the poorer alignment of the polymer thin films with lower side chain density. The study demonstrates that optimizing side chain density is a synthetically simple and effective way to improve electrical conductivity in polythiophene films relevant to thermoelectric applications.

Pyridine Functionalized Carbon Nanotubes: Unveiling the Role of External Pyridinic Nitrogen Sites for Oxygen Reduction Reaction.

Pyridinic nitrogen has been recognized as the primary active site in nitrogen-doped carbon electrocatalysts for the oxygen reduction reaction (ORR), which is a critical process in many renewable energy devices. However, the preparation of nitrogen-doped carbon catalysts comprised of exclusively pyridinic nitrogen remains challenging, as well as understanding the precise ORR mechanisms on the catalyst. Herein, a novel process is developed using pyridyne reactive intermediates to functionalize carbon nanotubes (CNTs) exclusively with pyridine rings for ORR electrocatalysis. The relationship between the structure and ORR performance of the prepared materials is studied in combination with density functional theory calculations to probe the ORR mechanism on the catalyst. Pyridinic nitrogen can contribute to a more efficient 4-electron reaction pathway, while high level of pyridyne functionalization result in negative structural effects, such as poor electrical conductivity, reduced surface area, and small pore diameters, that suppressed the ORR performance. This study provides insights into pyridine-doped CNTs-functionalized for the first time via pyridyne intermediates-as applied in the ORR and is expected to serve as valuable inspiration in designing high-performance electrocatalysts for energy applications.

Programmed Self-Assembly of DNA Nanosheets with Discrete Single-Molecule Thickness and Interfacial Mechanics: Design, Simulation, and Characterization.

DNA is programmed to hierarchically self-assemble into superstructures spanning from nanometer to micrometer scales. Here, we demonstrate DNA nanosheets assembled out of a rationally designed flexible DNA unit (F-unit), whose shape resembles a Feynman diagram. F-units were designed to self-assemble in two dimensions and to display a high DNA density of hydrophobic moieties. oxDNA simulations confirmed the planarity of the F-unit. DNA nanosheets with a thickness of a single DNA duplex layer and with large coverage (at least 30 µm × 30 µm) were assembled from the liquid phase at the solid/liquid interface, as unambiguously evidenced by atomic force microscopy imaging. Interestingly, single-layer nanodiscs formed in solution at low DNA concentrations. DNA nanosheet superstructures were further assembled at liquid/liquid interfaces, as demonstrated by the fluorescence of a double-stranded DNA intercalator. Moreover, the interfacial mechanical properties of the nanosheet superstructures were measured as a response to temperature changes, demonstrating the control of interfacial shear mechanics based on DNA nanostructure engineering. The rational design of the F-unit, along with the presented results, provide an avenue toward the controlled assembly of reconfigurable/responsive nanosheets and membranes at liquid/liquid interfaces, to be potentially used in the characterization of biomechanical processes and materials transport.

Click-Functionalization of Silanized Carbon Nanotubes: From Inorganic Heterostructures to Biosensing Nanohybrids.

Here we present an approach to functionalize silanized single-walled carbon nanotubes (SWNTs) through copper-free click chemistry for the assembly of inorganic and biological nanohybrids. The nanotube functionalization route involves silanization and strain-promoted azide-alkyne cycloaddition reactions (SPACC). This was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and Fourier transform infra-red spectroscopy. Silane-azide-functionalized SWNTs were immobilized from solution onto patterned substrates through dielectrophoresis (DEP). We demonstrate the general applicability of our strategy for the functionalization of SWNTs with metal nanoparticles (gold nanoparticles), fluorescent dyes (Alexa Fluor 647) and biomolecules (aptamers). In this regard, dopamine-binding aptamers were conjugated to the functionalized SWNTs to perform real-time detection of dopamine at different concentrations. Additionally, the chemical route is shown to selectively functionalize individual nanotubes grown on the surface of silicon substrates, contributing towards future nano electronic device applications.

Aqueous processing of organic semiconductors enabled by stable nanoparticles with built-in surfactants.

The introduction of oligoether side chains onto a polymer backbone can help to stabilise polymeric dispersions in water without the necessity of surfactants or additives when conjugated polymer nanoparticles are prepared. A series of poly(3-hexylthiophene) (P3HT) derivatives with different content of a polar thiophene derivative 3-((2-methoxyethoxy)methyl)thiophene was interrogated to find the effect of the polar chains on the stability of the formed nanoparticles, as well as their structural, optical, electrochemical, and electrical properties. Findings indicated that incorporation of 10-20 percent of the polar side chain led to particles that are stable over a period of 42 days, with constant particle size and polydispersity, however the particles from the polymer with 30 percent polar side chain showed aggregation effects. The polymer dispersions showed a stronger solid-like behaviour in water with decreasing polar side chain content, while thin film deposition from water was found to afford globular morphologies and crystallites with more isotropic orientation compared to conventional solution-processed films. As a proof-of-principle, field-effect transistors were fabricated directly from the aqueous dispersions demonstrating that polymers with hydrophilic moieties can be processed in water without the requirement of surfactants.

Nanoscale Control of DNA-Linked MoS2-Quantum Dot Heterostructures.

The ability to control the assembly of mixed-dimensional heterostructures with nanoscale control is key for the fabrication of novel nanohybrid systems with new functionalities, particularly for optoelectronics applications. Herein we report a strategy to control the assembly of heterostructures and tune their electronic coupling employing DNA as a linker. We functionalized MoS2 nanosheets (NSs) with biotin-terminated dsDNA employing three different chemical strategies, namely, thiol, maleimide, and aryl diazonium. This allowed us to then tether streptavidinated quantum dots (QDs) to the DNA functionalized MoS2 surface via biotin-avidin recognition. Nanoscale control over the separation between QDs and NSs was achieved by varying the number of base pairs (bp) constituting the DNA linker, between 10, 20, and 30 bp, corresponding to separations of 3.4, 6.8, and 13.6 nm, respectively. Spectroscopic data confirmed the successful functionalization, while atomic force and transmission electron microscopy were employed to image the nanohybrids. In solution steady-state and time-resolved photoluminescence demonstrated the electronic coupling between the two nanostructures, that in turn was observed to progressively scale as a function of DNA linker employed and hence distance between the two nanomoieties in the hybrids.

Antiferroelectric-like Behavior in a Lead-Free Perovskite Layered Structure Ceramic.

Antiferroelectric (AFE) materials have been intensively studied due to their potential uses in energy storage applications and energy conversion. These materials are characterized by double polarization-electric field (P-E) hysteresis loops and nonpolar crystal structures. Unusually, in the present work, Sr1.68La0.32Ta1.68Ti0.32O7 (STLT32), Sr1.64La0.36Ta1.64Ti0.36O7 (STLT36), and Sr1.85Ca0.15Ta2O7 (SCT15), lead-free perovskite layered structure (PLS) materials, are shown to exhibit AFE-like double P-E hysteresis loops despite maintaining a polar crystal structure. The double hysteresis loops are present over wide ranges of electric field and temperature. While neutron diffraction and piezoresponse force microscopy results indicate that the STLT32 system should be ferroelectric at room temperature, the observed AFE-like electrical behavior suggests that the electrical response is dominated by a weakly polar phase with a field-induced transition to a more strongly polar phase. Variable-temperature dielectric measurements suggest the presence of two-phase transitions in STLT32 at ca. 250 and 750 °C. The latter transition is confirmed by thermal analysis and is accompanied by structural changes in the layers, such as in the degree of octahedral tilting and changes in the perovskite block width and interlayer gap, associated with a change from non-centrosymmetric to centrosymmetric structures. The lower-temperature transition is more diffuse in nature but is evidenced by subtle changes in the lattice parameters. The dielectric properties of an STLT32 ceramic at microwave frequencies was measured using a coplanar waveguide transmission line and revealed stable permittivity from 1 kHz up to 20 GHz with low dielectric loss. This work represents the first observation of its kind in a PLS-type material.

Fabrication and Functionalisation of Nanocarbon-Based Field-Effect Transistor Biosensors.

Nanocarbon-based field-effect transistor (NC-FET) biosensors are at the forefront of future diagnostic technology. By integrating biological molecules with electrically conducting carbon-based platforms, high sensitivity real-time multiplexed sensing is possible. Combined with their small footprint, portability, ease of use, and label-free sensing mechanisms, NC-FETs are prime candidates for the rapidly expanding areas of point-of-care testing, environmental monitoring and biosensing as a whole. In this review we provide an overview of the basic operational mechanisms behind NC-FETs, synthesis and fabrication of FET devices, and developments in functionalisation strategies for biosensing applications.

Regulation of cardiomyocyte adhesion and mechanosignalling through distinct nanoscale behaviour of integrin ligands mimicking healthy or fibrotic extracellular matrix.

The stiffness of the cardiovascular environment changes during ageing and in disease and contributes to disease incidence and progression. Changing collagen expression and cross-linking regulate the rigidity of the cardiac extracellular matrix (ECM). Additionally, basal lamina glycoproteins, especially laminin and fibronectin regulate cardiomyocyte adhesion formation, mechanics and mechanosignalling. Laminin is abundant in the healthy heart, but fibronectin is increasingly expressed in the fibrotic heart. ECM receptors are co-regulated with the changing ECM. Owing to differences in integrin dynamics, clustering and downstream adhesion formation this is expected to ultimately influence cardiomyocyte mechanosignalling; however, details remain elusive. Here, we sought to investigate how different cardiomyocyte integrin/ligand combinations affect adhesion formation, traction forces and mechanosignalling, using a combination of uniformly coated surfaces with defined stiffness, polydimethylsiloxane nanopillars, micropatterning and specifically designed bionanoarrays for precise ligand presentation. Thereby we found that the adhesion nanoscale organization, signalling and traction force generation of neonatal rat cardiomyocytes (which express both laminin and fibronectin binding integrins) are strongly dependent on the integrin/ligand combination. Together our data indicate that the presence of fibronectin in combination with the enhanced stiffness in fibrotic areas will strongly impact on the cardiomyocyte behaviour and influence disease progression. This article is part of the theme issue 'The cardiomyocyte: new revelations on the interplay between architecture and function in growth, health, and disease'.

Engineering a DNA origami mediated multicolour quantum dot platform for sub-diffraction spectral separation imaging.

The validation of super-resolution optical imaging techniques requires well-defined reference samples that can be used repeatedly and reliably as model standards. Here, we engineer a DNA origami scaffold-mediated multicolour quantum dot hybrid nanostructure and test it using a recently proposed Quantum Dot-based spectral separation technique. We show that multivalent DNA structures offer a robust and precise nanoscale quantum dot placement scaffold, while the spectral resolution method provides relatively simple and fast image acquisition capabilities using any standard confocal or fluorescence microscope capable of spectral signal separation and a single excitation laser wavelength.

Grain Size Effects in Mn-Modified 0.67BiFeO3-0.33BaTiO3 Ceramics.

Grain size can have significant effects on the properties of electroceramics for dielectric, piezoelectric, and ferroelectric applications. Here, we systematically investigate the effect of grain size on the structure and properties of Mn-modified 0.67BiFeO3-0.33BaTiO3 ceramics, an important lead-free piezoelectric ceramic that exhibits both a high piezoelectric coefficient and a high Curie point. Ceramics with average grain sizes ranging from 0.46 to 6.85 µm were prepared using conventional and spark plasma sintering. It was found that the morphotropic phase boundary compositions are composed of two polar structures, rhombohedral and tetragonal, with DC poling inducing an increase in the fraction of the rhombohedral phase. All ceramics show relaxor behavior and their freezing temperature moves to higher temperatures with increasing grain size, although their Burns temperature is independent of grain size. In fine-grained ceramics, which show pronounced relaxor behavior, significant grain size dependency is seen in dielectric, piezoelectric, and ferroelectric properties, which is attributed to the presence of single ferroelectric domains and high concentrations of polar nanoregions. In coarse-grained ceramics, a critical grain size of 2.83 µm yields the highest dielectric permittivity at room temperature, with the piezoelectric coefficient plateauing at this grain size, which can be attributed to the contribution of both polar nanoregions and high domain wall density.

A Self-Powered Piezo-Bioelectric Device Regulates Tendon Repair-Associated Signaling Pathways through Modulation of Mechanosensitive Ion Channels.

Tendon disease constitutes an unmet clinical need and remains a critical challenge in the field of orthopaedic surgery. Innovative solutions are required to overcome the limitations of current tendon grafting approaches, and bioelectronic therapies show promise in treating musculoskeletal diseases, accelerating functional recovery through the activation of tissue regeneration-specific signaling pathways. Self-powered bioelectronic devices, particularly piezoelectric materials, represent a paradigm shift in biomedicine, negating the need for battery or external powering and complementing existing mechanotherapy to accelerate the repair processes. Here, the dynamic response of tendon cells to a piezoelectric collagen-analogue scaffold comprised of aligned nanoscale fibers made of the ferroelectric material poly(vinylidene fluoride-co-trifluoroethylene) is shown. It is demonstrated that motion-powered electromechanical stimulation of tendon tissue through piezo-bioelectric device results in ion channel modulation in vitro and regulates specific tissue regeneration signaling pathways. Finally, the potential of the piezo-bioelectronic device in modulating the progression of tendinopathy-associated processes in vivo, using a rat Achilles acute injury model is shown. This study indicates that electromechanical stimulation regulates mechanosensitive ion channel sensitivity and promotes tendon-specific over non-tenogenic tissue repair processes.

DNA-Directed Assembly of Carbon Nanotube-Protein Hybrids.

Here, we report the controlled assembly of SWCNT-GFP hybrids employing DNA as a linker. Two distinct, enriched SWCNTs chiralities, (6,5), (7,6), and an unsorted SWCNT solution, were selectively functionalized with DNA and hybridized to a complementary GFPDNA conjugate. Atomic force microscopy images confirmed that GFP attachment occurred predominantly at the terminal ends of the nanotubes, as designed. The electronic coupling of the proteins to the nanotubes was confirmed via in-solution fluorescence spectroscopy, that revealed an increase in the emission intensity of GFP when linked to the CNTs.

Tuning Electrostatic Gating of Semiconducting Carbon Nanotubes by Controlling Protein Orientation in Biosensing Devices.

The ability to detect proteins through gating conductance by their unique surface electrostatic signature holds great potential for improving biosensing sensitivity and precision. Two challenges are: (1) defining the electrostatic surface of the incoming ligand protein presented to the conductive surface; (2) bridging the Debye gap to generate a measurable response. Herein, we report the construction of nanoscale protein-based sensing devices designed to present proteins in defined orientations; this allowed us to control the local electrostatic surface presented within the Debye length, and thus modulate the conductance gating effect upon binding incoming protein targets. Using a ß-lactamase binding protein (BLIP2) as the capture protein attached to carbon nanotube field effect transistors in different defined orientations. Device conductance had influence on binding TEM-1, an important ß-lactamase involved in antimicrobial resistance (AMR). Conductance increased or decreased depending on TEM-1 presenting either negative or positive local charge patches, demonstrating that local electrostatic properties, as opposed to protein net charge, act as the key driving force for electrostatic gating. This, in turn can, improve our ability to tune the gating of electrical biosensors toward optimized detection, including for AMR as outlined herein.

DNA-driven dynamic assembly of MoS2 nanosheets.

Controlling the assembly of molybdenum disulfide (MoS2) layers into static and dynamic superstructures can impact on their use in optoelectronics, energy, and drug delivery. Toward this goal, we present a strategy to drive the assembly of MoS2 layers via the hybridization of complementary DNA linkers. By functionalizing the MoS2 surface with thiolated DNA, MoS2 nanosheets were assembled into mulitlayered superstructures, and the complementary DNA strands were used as linkers. A disassembly process was triggered by the formation of an intramolecular i-motif structure at a cystosine-rich sequence in the DNA linker at acidic pH values. We tested the versatility of our approach by driving the disassembly of the MoS2 superstructures through a different DNA-based mechanism, namely strand displacement. This study demonstrates how DNA can be employed to drive the static and dynamic assembly of MoS2 nanosheets in aqueous solution.

Tuning Electrostatic Gating of Semiconducting Carbon Nanotubes by Controlling Protein Orientation in Biosensing Devices.

The ability to detect proteins through gating conductance by their unique surface electrostatic signature holds great potential for improving biosensing sensitivity and precision. Two challenges are: (1) defining the electrostatic surface of the incoming ligand protein presented to the conductive surface; (2) bridging the Debye gap to generate a measurable response. Herein, we report the construction of nanoscale protein-based sensing devices designed to present proteins in defined orientations; this allowed us to control the local electrostatic surface presented within the Debye length, and thus modulate the conductance gating effect upon binding incoming protein targets. Using a ß-lactamase binding protein (BLIP2) as the capture protein attached to carbon nanotube field effect transistors in different defined orientations. Device conductance had influence on binding TEM-1, an important ß-lactamase involved in antimicrobial resistance (AMR). Conductance increased or decreased depending on TEM-1 presenting either negative or positive local charge patches, demonstrating that local electrostatic properties, as opposed to protein net charge, act as the key driving force for electrostatic gating. This, in turn can, improve our ability to tune the gating of electrical biosensors toward optimized detection, including for AMR as outlined herein.

Single-molecule DNA origami aptasensors for real-time biomarker detection.

Here we report the use of DNA nanostructures as platforms to monitor the inherent conformational changes of aptamers upon analyte binding, with single-molecule resolution and real-time capability. An aptasensor designed to sense cortisol was found to suffer from instability in solution, but this was reconciled via a rational design of a single-molecule sensing platform. In this regard, DNA origami was employed to immobilise individual aptasensors on a glass surface and to ensure adequate interaction with their environment, for single-molecule analysis. The strategy presented here can be applied to any aptamer obtained by the destabilisation of a duplex in a SELEX process, and hence employed in the rational design of single-molecule biosensors.