Organic Photovoltaic Sensors for Photocapacitive Stimulation of Voltage‐Gated Ion Channels in Neuroblastoma Cells

Organic semiconductors are emerging as promising candidates for novel electrically self‐sufficient photovoltaic prosthetics for neurostimulation, especially for restoration of light sensitivity in degenerate retina. Considering future applications, it is essential to gain fundamental insight into the signaling mechanisms at the organic photosensor–electrolyte–neuron interface. Particularly, targeting voltage‐gated ion channels by a pure photocapacitive stimulation is a preferred therapeutic approach as it avoids redox reactions involved in Faradaic charge injection. The present study investigates whether single neuroblastoma (N2A) cells, grown on a photosensor based on a small molecular squaraine:fullerene photoactive layer blend, optionally covered with silicon dioxide, can be activated by photocapacitive stimulation. Indeed, upon pulsed illumination, a rapid transient photocurrent strongly depolarizes the membrane potential and subsequently activates fast‐responding voltage‐gated sodium channels. The dielectric top coating on the organic layer ensures sufficient capacitive charge injection efficiency while maintaining the rapid response of the device. Due to the high irradiance level required for photocapacitive stimulation, another slower, independent, and unintended, nonelectrical signaling pathway is identified. This activates voltage‐gated potassium channels, presumably by photothermal effects. The present study provides the basis for further improvements on standalone photovoltaic neurostimulating platforms based on organic photoactive layers.     

3D Carbon Nanotube Network Bridged Hetero‐Structured Ni‐Fe‐S Nanocubes toward High‐Performance Lithium,Sodium, and Potassium Storage

Lithium‐ion, sodium‐ion, and potassium‐ion batteries have captured tremendous attention in power supplies for various electric vehicles and portable electronic devices. However, their practical applications are severely limited by factors such as poor rate capability, fast capacity decay, sluggish charge storage dynamics, and low reversibility. Herein, hetero‐structured bimetallic sulfide (NiS/FeS) encapsulated in N‐doped porous carbon cubes interconnected with CNTs (Ni‐Fe‐S‐CNT) are prepared through a convenient co‐precipitation and post‐heat treatment sulfurization technique of the corresponding Prussian‐blue analogue nanocage precursor. This special 3D hierarchical structure can offer a stable interconnect and conductive network and shorten the diffusion path of ions, thereby greatly enhancing the mobility efficiency of alkali (Li, Na, K) ions in electrode materials. The Ni‐Fe‐S‐CNT nanocomposite maintains a charge capacity of 1535 mAh g^?1 at 0.2 A g^?1 for lithium ion batteries, 431 mAh g^?1 at 0.1 A g^?1 for sodium ion batteries, and 181 mAh g^?1 at 0.1 A g^?1 for potassium‐ion batteries, respectively. The high performance is mainly attributed to the 3D hierarchically high‐conductivity network architecture, in which the hetero‐structured FeS/NiS nanocubes provide fast Li⁺/Na⁺/K⁺ insertion/extraction and reduced ion diffusion paths, and the distinctive 3D networks maintain the electrical contact and guarantee the structural integrity.     

Multifurcate Assembly of Slanted Micropillars Fabricated by Superposition of Optical Vortices and Application in High‐Efficiency Trapping Microparticles

Self‐assembly induced by capillary force is abundant in nature and has been widely used in fabrication as a bottom‐up method. Here a rapid and flexible method for achieving an even number of furcate slanted micropillars by single‐exposure under a spatial phase modulated laser beam is reported, which is produced by designing a superimposed hologram with opposite topological charges to split the incident beam into several equal‐weighting sectors. These furcate micropillars with intentional spatial arrangement can be directed to capillary‐assisted self‐assembly process for generating designable hierarchical functional arrays. Due to the slanted characteristic of micropillars (8°–13°), the assembled arrays are very stable and can be used as an effective tool for trapping SiO₂ particles to form honeycomb patterns with an ultrahigh trapping ratio (>90%), which can image as a microlens array. The investigation reveals that micropillars with a height of 6 µm exhibit the high trapping ratio of particles, which maintain a fine imaging performance. The fast fabrication (more than 2 orders of magnitude enhancement) of furcate slanted pillars paves an avenue for developing innovative microoptics, microfluidics and biological scaffold engineering.     

High‐Yield Fabrication and Electrochemical Characterization of Tetrapodal CdSe,CdTe, and CdSexTe1–x Nanocrystals

The high‐yield fabrication of tetrapodal CdSe, CdTe, and CdSe_xTe_1–x nanocrystals is systematically studied. CdSe nanocrystals are prepared by first controlling the synthesis of high‐quality wurtzite CdSe and zinc blende CdSe nanocrystals at a relatively high temperature (260 °C) by selecting different ligands. Then, based on the phase control of the CdSe nanocrystals, two nanoparticle‐tailoring routes (i.e., a seed‐epitaxial route and ligand‐dependent multi‐injecting route) are used, and a high yield of CdSe tetrapods is obtained. CdTe nanocrystals are prepared by adjusting the ligand composition and the ratio of Cd to Te; CdTe tetrapods are synthesized in high yield using a mixed ligand that does not contain alkylphosphonic acids. Moreover, the nanoscale Te powder (Te nanowires/nanorods), which is highly soluble in the ligand solvent, is first used as a Te source to synthesize CdTe nanocrystals, which remarkably enhanced the output of the CdTe nanocrystals in one reaction. Furthermore, composition‐tunable ternary CdSe_xTe_1–x alloyed tetrapods are synthesized on a large scale, for the first time, by thermolyzing the mixture of the organometallic Cd precursor and the mixed (Se + Te) source in a mixed‐ligand solution. The CdSe, CdTe, and CdSe_xTe_1–x nanocrystals are characterized by transmission electron microscopy (TEM), high‐resolution TEM, selected‐area electron diffraction, X‐ray diffraction, and UV‐vis and photoluminescence (PL) spectroscopy. Interesting nonlinear, composition‐dependent absorption and PL spectra are observed for the ternary CdSe_xTe_1–x alloyed nanocrystals. The band‐edge positions of the nanocrystals of CdSe, CdSe_xTe_1–x, and CdTe are systematically studied by cyclic voltammetry.     

General Method for Large‐Area Films of Carbon Nanomaterials and Application of a Self‐Assembled Carbon Nanotube Film as a High‐Performance Electrode Material for an All‐Solid‐State Supercapacitor

Rational assembly of carbon nanostructures into large‐area films is a key step to realize their applications in ubiquitous electronics and energy devices. Here, a self‐assembly methodology is devised to organize diverse carbon nanostructures (nanotubes, dots, microspheres, etc.) into homogeneous films with potentially infinite lateral dimensions. On the basis of studies of the redox reactions in the systems and the structures of films, the spontaneous deposition of carbon nanostructures onto the surface of the copper substrate is found to be driven by the electrical double layer between copper and solution. As a notable example, the as‐assembled multiwalled carbon nanotube (MWCNT) films display exceptional properties. They are a promising material for flexible electronics with superior electrical and mechanical compliance characteristics. Finally, two kinds of all‐solid‐state supercapacitors based on the self‐assembled MWCNT films are fabricated. The supercapacitor using carbon cloth as the current collector delivers an energy density of 3.5 Wh kg^?1 and a power density of 28.1 kW kg^?1, which are comparable with the state‐of‐the‐art supercapacitors fabricated by the costly single‐walled carbon nanotubes and arrays. The supercapacitor free of foreign current collector is ultrathin and shows impressive volumetric energy density (0.58 mWh cm^?3) and power density (0.39 W cm^?3) too.     

Mechanical Properties and Flame‐Retardant Behavior of Ethylene Vinyl Acetate/High‐Density Polyethylene Coated Carbon Nanotube Nanocomposites

High‐density polyethylene coated multiwalled carbon nanotubes (c‐MWNTs) and multiwalled carbon nanotubes (MWNTs) have been dispersed into an ethylene vinyl acetate (EVA) copolymer by mechanical kneading. The effect of c‐MWNTs on tensile properties, thermo‐oxidative degradation, and fire behavior has been studied in comparison with virgin EVA and EVA/MWNTs nanocomposites. Due to the better dispersion of the coated nanotubes, the incorporation of 3 wt % of c‐MWNTs leads to an increase of the Young's modulus, the cohesion of the combustion residues, and a decrease of the peak heat‐release rate.     

Versatile,High‐Power,Flexible, Stretchable Carbon Nanotube Sheet Heating Elements Tolerant to Mechanical Damage and Severe Deformation

A macroscopic carbon nanotube (CNT) sheet‐based heating element having flexible, stretchable, and damage‐tolerant features, and wide applicability in harsh environments, is introduced. Because of the intrinsic connection of extremely flexible CNT bundles throughout the sample by van der Waals interactions without use of a binder, the electrical resistance variation of the CNT sheet on elastomer heating element as a function of strain is completely suppressed to some extent, even when stretched under up to 400% strain, which guarantees electrical stability under severe mechanical deformation. In addition, the spatial uniformity of the heat generated from the microaligned CNT bundles reduces the temperature variation inside the sample, which also guarantees thermal stability and operation at a higher average temperature. Such exceptional performance is achieved by the passivation of the elastomer layer on the CNT sheets. Furthermore, the mechanical robustness of this flexible, stretchable heating element is demonstrated by stable heater operation, even when the heating element is damaged. In addition, this design concept of CNT sheet on elastomer is extended to transparent flexible heaters and electric‐thermochromic windows.     

MoSe2‐Covered N,P‐Doped Carbon Nanosheets as a Long‐Life and High‐Rate Anode Material for Sodium‐Ion Batteries

MoSe₂ grown on N,P‐co‐doped carbon nanosheets is synthesized by a solvothermal reaction followed with a high‐temperature calcination. This composite has an interlayer spacing of MoSe₂ expanded to facilitate sodium‐ion diffusion, MoSe₂ immobilized on carbon nanosheets to improve charge‐transfer kinetics, and N and P incorporated into carbon to enhance its interaction with active species upon cycling. These features greatly improve the electrochemical performance of this composite, as compared to all the controls. It presents a specific capacity of 378 mAh g^?1 after 1000 cycles at 0.5 A g^?1, corresponding to 87% of the capacity at the second cycle. Ex situ Raman spectra and high‐resolution transmission electron microscopy images confirm that it is element Se, rather than MoSe₂, formed after the charging process. The interaction of the active species with modified carbon is simulated using density functional theory to explain this excellent stability. The superior rate capability, where the capacity at 15 A g^?1 equals ≈55% of that at 0.5 A g^?1, could be associated with the significant contribution of pseudocapacitance. By pairing with homemade Na₃V₂(PO₄)₃/C, this composite also exhibits excellent performances in full cells.     

Nitrogen‐Doped Mesoporous Carbon Promoted Chemical Adsorption of Sulfur and Fabrication of High‐Areal‐Capacity Sulfur Cathode with Exceptional Cycling Stability for Lithium‐Sulfur Batteries

As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm^‐2 with a high sulfur loading (4.2 mg S cm^‐2) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm^‐2) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries.     

A Composite of Carbon‐Wrapped Mo2C Nanoparticle and Carbon Nanotube Formed Directly on Ni Foam as a High‐Performance Binder‐Free Cathode for Li‐O2 Batteries

Cathode design is indispensable for building Li‐O₂ batteries with long cycle life. A composite of carbon‐wrapped Mo₂C nanoparticles and carbon nanotubes is prepared on Ni foam by direct hydrolysis and carbonization of a gel composed of ammonium heptamolybdate tetrahydrate and hydroquinone resin. The Mo₂C nanoparticles with well‐controlled particle size act as a highly active oxygen reduction reactions/oxygen evolution reactions (ORR/OER) catalyst. The carbon coating can prevent the aggregation of the Mo₂C nanoparticles. The even distribution of Mo₂C nanoparticles results in the homogenous formation of discharge products. The skeleton of porous carbon with carbon nanotubes protrudes from the composite, resulting in extra voids when applied as a cathode for Li‐O₂ batteries. The batteries deliver a high discharge capacity of ≈10 400 mAh g^?1 and a low average charge voltage of ≈4.0 V at 200 mA g^?1. With a cutoff capacity of 1000 mAh g^?1, the Li‐O₂ batteries exhibit excellent charge–discharge cycling stability for over 300 cycles. The average potential polarization of discharge/charge gaps is only ≈0.9 V, demonstrating the high ORR and OER activities of these Mo₂C nanoparticles. The excellent cycling stability and low potential polarization provide new insights into the design of highly reversible and efficient cathode materials for Li‐O₂ batteries.     

One‐Step Self‐Assembly Fabrication of High Quality NixMg1‐xO Bowl‐Shaped Array Film and Its Enhanced Photocurrent by Mg,2+ Doping

A series of high quality Ni_xMg_1‐xO bowl‐shaped array films are successfully prepared by a simple one‐step assembly of polystyrene colloidal spheres and metal oxide precursors at oil–water interface, and further used to fabricate nanodevices. The doping of Mg²⁺ can greatly enhance the current and spectrum responsivity of NiO film‐based nanodevice. The maximum R_λ value of these bowl‐shaped Ni_xMg_1‐xO film‐based devices measured in the study shows 4–5 orders of enhancement than the previously reported Ni_xMg_1‐xO film at equal doping.     

A High‐Energy Lithium‐Ion Capacitor by Integration of a 3D Interconnected Titanium Carbide Nanoparticle Chain Anode with a Pyridine‐Derived Porous Nitrogen‐Doped Carbon Cathode

Lithium‐ion capacitors (LICs) are hybrid energy storage devices that have the potential to bridge the gap between conventional high‐energy lithium‐ion batteries and high‐power capacitors by combining their complementary features. The challenge for LICs has been to improve the energy storage at high charge?discharge rates by circumventing the discrepancy in kinetics between the intercalation anode and capacitive cathode. In this article, the rational design of new nanostructured LIC electrodes that both exhibit a dominating capacitive mechanism (both double layer and pseudocapacitive) with a diminished intercalation process, is reported. Specifically, the electrodes are a 3D interconnected TiC nanoparticle chain anode, synthesized by carbothermal conversion of graphene/TiO₂ hybrid aerogels, and a pyridine‐derived hierarchical porous nitrogen‐doped carbon (PHPNC) cathode. Electrochemical properties of both electrodes are thoroughly characterized which demonstrate their outstanding high‐rate capabilities. The fully assembled PHPNC//TiC LIC device delivers an energy density of 101.5 Wh kg^?1 and a power density of 67.5 kW kg^?1 (achieved at 23.4 Wh kg^?1), and a reasonably good cycle stability (≈82% retention after 5000 cycles) within the voltage range of 0.0?4.5 V.     

Enhanced Performance of Self‐Assembled Monolayer Field‐Effect Transistors with Top‐Contact Geometry through Molecular Tailoring,Heated Assembly,and Thermal Annealing

Low‐voltage self‐assembled monolayer field‐effect transistors (SAMFETs) that operate under an applied bias of less than ?3 V and a high hole mobility of 10^?2 cm² V^?1 s^?1 are reported. A self‐assembled monolayer (SAM) with a quaterthiophene semiconducting core and a phosphonic acid binding group is used to fabricate SAMFETs on both high‐voltage (AlO_x/300 nm SiO₂) and low‐voltage (HfO₂) dielectric platforms. High performance is achieved through enhanced SAM packing density via a heated assembly process and through improved electrical contact between SAM semiconductor and metal electrodes. Enhanced electrical contact is obtained by utilizing a functional methylthio head group combined with thermal annealing post gold source/drain electrode deposition to facilitate the interaction between SAM and electrode.     

Formation of Nanoislands on Conducting Poly(3,4‐ethylenedioxythiophene) Films by High‐Energy‐Ion Irradiation: Applications as Field Emitters and Capacitor Electrodes

Nanoislands have been fabricated on the surface of conducting poly(3,4‐ethylenedioxythiophene) (PEDOT) films doped with poly(4‐styrenesulfonate) (PSS) using high‐energy (≈ 1–3 MeV) Cl²⁺ ion irradiation. Scanning electron microscopy and atomic force microscopy confirm the direct formation of nanoislands with diameters ranging from 50 to 300 nm and heights ranging from 40 to 120 nm. From our analysis, we propose that the formation of nanoislands might be due to micelle formation of the polymeric stabilizer poly(sodium 4‐styrenesulfonate) (PSS‐Na) surrounding the nuclei in the PEDOT/PSS via the high‐energy‐ion irradiation. We observe similar results for high‐energy‐ion irradiated polyaniline doped with PSS‐Na. On using the nanoislands as nanotip emitters of a field‐emission display, an increase in the current density of about five orders of magnitude is observed. Cyclic voltammetry of the PEDOT/PSS electrode with the nanoislands as the electrode shows enhanced capacitance compared with that of the PEDOT/PSS film that contains no nanostructure.     

Fabrication and Surface Functionalization of Nanoporous Gold by Electrochemical Alloying/Dealloying of Au–Zn in an Ionic Liquid,and the Self‐Assembly of L‐Cysteine Monolayers

This paper describes a totally electrochemical process for the fabrication and functionalization of high‐surface‐area, nanoporous gold films. The fabrication process involves the electrodeposition of a binary gold–zinc alloy at gold wires, followed by subsequent electrochemical dealloying of the less noble component zinc from the surface. Both the deposition and dealloying steps are conducted in a single low‐temperature bath of 40.0–60.0 mol‐% zinc chloride–1‐ethyl‐3‐methylimidazolium chloride ionic liquid at 120 °C without using any other corrosive acids or bases. The porous structure and morphology of the nanostructured gold film could be controlled by electrochemical variation of the composition of the Au–Zn surface alloy. It is demonstrated that the nanoporous gold surface can be successfully functionalized with self‐assembled monolayers of L ‐cysteine. Such functionalization greatly improves the utility of the nanoporous gold, as is demonstrated in the sensitive and selective determination of Cu(II ).     

In Situ Generated Gas Bubble‐Directed Self‐Assembly: Synthesis,and Peculiar Magnetic and Electrochemical Properties of Vertically Aligned Arrays of High‐Density Co3O4 Nanotubes

A novel and versatile gas bubble induced self‐assembly technique is developed for the one‐step fabrication of vertically aligned polycrystalline Co₃O₄ nanotube arrays (NTAs) by the rapid thermal decomposition of Co(NO₃)₂·6H₂O on a flat substrate. In this protocol, the in situ generation and release of gas bubbles, which can be regulated by elaborately adjusting the kinetic factors such as reaction time, decomposition temperature and pressure as well as the content of the chemically adsorbed water, play a vital role in the formation of the Co₃O₄ NTAs. Due to the shape anisotropy, ordered hierarchically porous structure and high surface area, the as‐obtained Co₃O₄ NTAs show unique magnetic properties of a low Néel temperature and a large exchange bias field, as well as an initial discharge capacity up to 1293 mAh·g^?1 at 35 mA·g^?1 and the retention of a charge capacity as high as 895.4 mAh·g^?1 after 10 cycles. This endows them with important potential use in magnetic shielding, magnetic recording media, and lithium ion batteries, etc. Due to the simplicity of the self‐assembly method, this process is applicable to the large‐scale production of the Co₃O₄ NTAs, and may be extended to other materials.     

Quantum‐Dot‐Functionalized Poly(styrene‐co‐acrylic acid) Microbeads: Step‐Wise Self‐Assembly,Characterization, and Applications for Sub‐femtomolar Electrochemical Detection of DNA Hybridization

A novel nanoparticle label capable of amplifying the electrochemical signal of DNA hybridization is fabricated by functionalizing poly(styrene‐co‐acrylic acid) microbeads with CdTe quantum dots. CdTe‐tagged polybeads are prepared by a layer‐by‐layer self‐assembly of the CdTe quantum dots (diameter = 3.07 nm) and polyelectrolyte on the polybeads (diameter = 323 nm). The self‐assembly procedure is characterized using scanning and transmission electron microscopy, and X‐ray photoelectron, infrared and photoluminescence spectroscopy. The mean quantum‐dot coverage is (9.54 ± 1.2) × 10³ per polybead. The enormous coverage and the unique properties of the quantum dots make the polybeads an effective candidate as a functionalized amplification platform for labelling of DNA or protein. Herein, as an example, the CdTe‐tagged polybeads are attached to DNA probes specific to breast cancer by streptavidin–biotin binding to construct a DNA biosensor. The detection of the DNA hybridization process is achieved by the square‐wave voltammetry of Cd²⁺ after the dissolution of the CdTe tags with HNO₃. The efficient carrier‐bead amplification platform, coupled with the highly sensitive stripping voltammetric measurement, gives rise to a detection limit of 0.52 fmol L^?1 and a dynamic range spanning 5 orders of magnitude. This proposed nanoparticle label is promising, exhibits an efficient amplification performance, and opens new opportunities for ultrasensitive detection of other biorecognition events.