Fabricating Nanogaps between Nanoelectrodes using Dielectrophoresis Technique for Molecular Fluorescence Enhancement

Here we demonstrate the fabrication of nanometer-sized gaps by assembling single coreshell nanoparticles between metallic nanoelectrodes. Protein coated SiO2@Au coreshell nanopar- tides arc synthesized and positioned between fluorescent molecules-covered electrodes in a controllable way using dielectrophoretic trapping, forming nanogaps sandwiched between nanoparticle and manoelectrodes. Preliminary photoluminescence measurements show that enhanced molecular fluorescence could be detected from the fluorescent molecules inside the nanogaps. These results pave the way for realizing electrically driven molecular fluorescence based on nanogap electrodes.

Self-assembly of Gold Nanoparticle Chains between Nanoelectrodes

A novel strategy has been developed for construction of nanoparticle chains between nanoelectrodes with bifunctional molecules by taking advantage of linear aggregation of colloidal particles in organis solvents. As confirmed by scanning electron microscopy （SEM）,an individual nanoparticle chain bridged the electrode pair. The present approach makes this technique to be cheap and may be applicable in microelectronic industry.

A Simple Method for Fabrication of Gold Nanoelectrodes

A facile method has been developed for the fabrication of Au nanoelecrodes (Au NEs). The tip of Au NEs can be controlled within the range from dozens to hundreds of nanometer.

Electrofluorochromic imaging analysis of dopamine release from living PC12 cells with bipolar nanoelectrodes array

The coupling of bipolar electrode(BPE)arrays and electrofluorochromic(EFC)imaging has exhibited great abilities in bioanalysis.However,the imaging resolution and analytical performance are hampered by the large size of the electrode and the rapid diffusion of EFC molecules on the electrode surface.Here,to address the challenges,bipolar nanoelectrodes(BPn E)array and in situ immobilization strategy of EFC molecules were proposed.Anodized aluminum oxide(AAO)template-assisted Au nanoelectrodes array with high density was fabricated as BPn E array for high spatial imaging resolution.By electrically polymerizing EFC molecules on the surface of single Au nanoelectrode,the rapid diffusion of EFC molecules on the electrode surface was not only avoided,but also realizing electrofluorescent imaging on an individual nanoelectrode.Using dopamine(DA)released from living PC12 cells as a model,the proposed strategy exhibited an ultra-high sensitivity for DA analysis with a detection limit of 0.45 nmol/L and the DA release amount from a single cell was calculated to be 0.13 pmol/L.Moreover,the dynamic change of DA release under the drug stimulation from living PC12 cells could also be monitored.

Fabrication and characteristic detection of graphene nanoelectrodes

Graphene has the advantages of high electrical conductivity,high heat conductivity,and low noise,which makes it a potential option for integrated circuits interconnection and nanoelectrodes.In this paper,we present a novel fabrication method for graphene nanoeletrodes with nanogap.First,graphene grown by chemical vapor deposition(CVD)is assembled to a chip with microelectrodes.Second,an atomic force microscopy(AFM)based mechanical cutting method is developed to cut the graphene into nanoribbons and nanoeletrodes with nanogap.Then the electronic property of a single nanodot is characterized using the garphene nanoelectrodes,demonstrating the effectiveness of the graphene nanoelectrodes.The fabricated graphene nanoeletrode pairs can be used as probes to detect single molecule in micro-environment,and show an attractive prospect for future molecular electronics applications.

Polarization Band Effect and MEMS-Based Plasma Generation

We find that effects resulting from micro/nano scale structures can regulate space charges which excite and lead to the special electric field distribution featuring the flux convergence band structure. It is here referred to as the polarization band effect, which stems from the specific field-induced interactions among atoms and molecules. The micro/nanoelectrode array structures were designed and fabricated using the non-silicon micro/nano processing technology, forming micro/nano electrode arrays-based plasma microelectromechanical systems(NPMEMS). The integrated NPMEMS device can be used to regulate the inner energy states of matters and generate plasma based on the polarization band effect, all within a single chip-size limited local area or extending into a large volume space with the deployment of a distributed array of multiple devices. Its special physical and chemical properties can be utilized to greatly improve the efficiency of potential application systems or solve mechanism-level challenges in plasma-related applications of multiple fields.

Recent Advances of Nanoelectrodes for Single-Cell Electroanalysis:From Extracellular, Intercellular to Intracellular

Detection at single-cell level plays a critical role in revealing cell behavior in different organisms.Nanoelectrodes with high temporal–spatial resolution can precisely and dynamically monitor the physiological and pathological processes of various single cells.The field of using nanoelectrodes in single-cell electroanalysis is blooming in recent years.In this review,we mainly summarize the recent advances of nanoelectrodes for single-cell electroanalysis from extracellular,intercellular to intracellular levels in the past decade.First,we introduce the main types of nanoelectrodes based on their geometry and characteristics for single-cell electroanalysis.Then,the representative works of using nanoelectrodes to investigate cellular signaling biomolecules and to understand various cellular processes from the extracellular,intercellular,and intracellular levels are introduced.Finally,the challenges and future prospects of nanoelectrodes for single-cell electroanalysis are proposed.This review gives a comprehensive summary of nanoelectrodes for single-cell electroanalysis in the prospects of monitoring cell physiological topography,understanding communication mechanism and revealing physiological functions,which can provide new insights into cell-based pharmacological screening and fundamental studies of disease development mechanisms.

Preparation of Nanoelectrode Ensembles by Assembly of Nano-Silver Colloid on Gold Surface

A novel method for preparing silver nanoelectrode ensembles (SNEEs) and gold nanoelectrode ensembles (GNEEs) has been developed. Silver colloid particles were first absorbed to the gold electrode surface to form a monolayer silver colloid. N-hexadecyl mercaptan was then assembled on the electrode to form a thiol monolayer on which hydrophilic ions cannot be transfered. The SNEEs was prepared by removing thiol from silver colloid surface through applying an AC voltage with increasing frequency at 0.20 V (vs. SCE). Finally, GNEEs was obtained by immersing a SNEEs into 6 mol/L HNO3 to remove the silver colloid particles. By comparison with other methods such as template method etc., this method enjoys some advantages of lower resistance, same diameter, easy preparation, controllable size and density.

Aligned carbon nanostructures based 3D electrodes for energy storage

Electrochemical energy storage systems with high specific energy and power as well as long cyclic stability attract increasing attention in new energy technologies. The principles for rational design of electrodes are discussed to reduce the activation, concentration, and resistance overpotentials and improve the active ma- terial efficiency in order to simultaneously achieve high specific energy and power. Three dimensional （3D） nanocomposites are currently considered as promising electrode materials due to their large surface area, reduced electronic and ionic diffusion distances, and synergistic effects. This paper reviews the most recent progress on the synthesis and application of 3D thin film nanoelectrode arrays based on aligned carbon nan- otubes （ACNTs） directly grown on metal foils for energy storages and special attentions are paid on our own representative works. These novel 3D nanoelectrode arrays on metal foil exhibit improved electrochemical performances in terms of specific energy, specific power and cyclic stability due to their unique structures. In this active materials coated ACNTs over conductive substrate structures, each component is tailored to address a different demand. The electrochemical active material is used to store energy, while the ACNTs are employed to provide a large surface area to support the active material and nanocable arrays to facilitate the electron transport. The thin film of active materials can not only reduce ion transport resistance by shorten- ing the diffusion length but also make the film elastic enough to tolerate significant volume changes during charge and discharge cycles. The conductive substrate is used as the current collector and the direct contact of the ACNT arrays with the substrate reduces significantly the contact resistance. The principles obtained from ACNT based electrodes are extended to aligned graphene based electrodes. Similar improvements have been achieved which confirms the reliability of the principles obtained. In addition, we also discuss and view the ongoing trends in development of aligned carbon nanostructures based electrodes for energy storage.

Micro/nanoelectrode-based electrochemical methodology for single cell and organelle analysis

Cells are the basic unit of life.Electrochemical analysis of single cells/organelles is essential for uncovering the molecular mechanisms of physiological and pathological processes that are difficult to elucidate on a larger scale.This paper provides an overview of the commonly used fabrication methods for micro/nanoelectrodes applied in the investigations of single cells/organelles as well as the corresponding electrochemical measurements over the last four years including extracellular measurement,combination of extra and intracellular measurement,intracellular reactive oxygen species and reactive nitrogen species(ROS/RNS)measurement,and isolated organelles measurement.

ChemFET gas nanosensor arrays with alignment windows for assembly of single nanowires

This work focuses on the fabrication and characterization of Chemical Field-Effect Transistor(ChemFET)gas nanosensor arrays based on single nanowire(SNW).The fabrication processes include micro and nanofabrication techniques enabled by a combination of ultraviolet(UV)and e-beam lithography to build the ChemFET structure.Results show the integration and connection of SNWs across the multiple pairs of nanoelectrodes in the ChemFET by dielectrophoresis process(DEP)thanks to the incorporation of alignment windows(200-300 nm)adapted to the diameter of the NWs.Measurements of the SNW ChemFET array's output and transfer characteristics prove the influence of gate bias on the drain current regulation.Tests upon hydrogen(H_(2))and nitrogen dioxide(NO_(2))as analyte models of reducing and oxidizing gases show the ChemFET sensing functionality.Moreover,results demonstrate better response characteristics to H_(2)when the ChemFET operates in the subthreshold regime.The design concepts and methods proposed for fabricating the SNW-based ChemFET arrays are versatile,reproducible,and most likely adaptable to other systems where SNW arrays are required.

Real-Time and Spatial Electroanalysis of Biomolecules in One Living Cell Using Liquid-Phase Modified Nanopipette

The well-developed solid-phase modified strategy at the electrode has enabled the preparation of biosensors for the detection of multiple analytes,even in single living cells.However,limited assay elements can be modified at the solid surface,restricting the types of molecules that can be analyzed and the sensitivity of detection.Here,a novel liquid-phase modified strategy at the tip of a nanopipette is designed to realize real-time and local analysis of biomolecules inside the cell that are barely detectable using solid-phase modified nanoelectrodes.This design utilizes the nanotip structure at a platinized carbon open nanopipette to stably retain a nanodroplet that contains the required reagents with high reactivity for the assay of the target analyte.The generated hydrogen peroxide is electrochemically quantified at the Pt layer to carry out the real-time measurement in a living cell with a spatial resolution of 70 nm.Taking advantage of highly spatial and real-time detection,uneven distribution of sphingomyelinase(SMase)in the living CT26 cell is unprecedentedly shown to exhibit the significance in the establishment of liquid-phase modified nanopipette.This new modification strategy opens up a new direction for sensor design and consequently advances the development of biosensors in the chemical and biological research.

Nano functional neural interfaces

Engineered functional neural interfaces （fNIs） serve as essential abiotic-biotic transducers between an engineered system and the nervous system. They convert external physical stimuli to cellular signals in stimulation mode or read out biological processes in recording mode. Information can be exchanged using electricity, light, magnetic fields, mechanical forces, heat, or chemical signals. fNIs have found applications for studying processes in neural circuits from cell cultures to organs to whole organisms, fNI-facilitated signal transduction schemes, coupled with easily manipulable and observable external physical signals, have attracted considerable attention in recent years. This enticing field is rapidly evolving toward miniaturization and biomimicry to achieve long-term interface stability with great signal transduction efficiency. Not only has a new generation of neuroelectrodes been invented, but the use of advanced fNIs that explore other physical modalities of neuromodulation and recording has begun to increase. This review covers these exciting developments and applications of fNIs that rely on nanoelectrodes, nanotransducers, or bionanotransducers to establish an interface with the nervous system. These nano fNIs are promising in offering a high spatial resolution, high target specificity, and high communication bandwidth by allowing for a high density and count of signal channels with minimum material volume and area to dramatically improve the chronic integration of the fNI to the target neural tissue. Such demanding advances in nano fNIs will greatly facilitate new opportunities not only for studying basic neuroscience but also for diagnosing and treating various neurological diseases.

Nanofabrication of the gold scanning probe for the STM-SECM coupling system with nanoscale spatial resolution

Scanning probe is the key issue for the electrochemical scanning probe techniques(EC-SPM) such as EC-scanning tunnel microscopy(STM), EC-atomic force microscopy(AFM) and scanning electrochemical microscopy(SECM), especially the insulative encapsulation of the nanoelectrode probe for both positioning and electrochemical feedbacks. To solve this problem,we develop a novel fabrication method of the gold nanoelectrodes: firstly, a micropipette with nanomter-sized orifice was prepared as the template by a laser puller; secondly, the inside wall of micropipette apex was blocked by compact and conic Au nano-piece through electroless plating; thirdly, the Au nano-piece was grown by bipolar electroplating and connected with a silver wire as a current collector. The fabricated Au nanoelectrode has very good voltammetric responses for the electrodic processes of both mass transfer and adsorption. The advantage lies in that it is well encapsulated by a thin glass sealing layer with a RG value lowered to 1.3, which makes it qualified in the SECM-STM coupling mode. On one hand, it can serve as STM tip for positioning which ensures the high spatial resolution; on the other hand, it is a high-quality nanoelectrode to explore the local chemical activity of the substrate. The nanofabrication method may promote the SPM techniques to obtain simultaneously the physical and chemical images with nanoscale spatial resolution, which opens a new approach to tip chemistry in electrochemical nanocatalysis and tip-enhanced spectroscopy.

Imaging resolution of biocatalytic activity using nanoscale scanning electrochemical microscopy

Scanning electrochemical microscopy represents a powerful tool for electro（chemical） characterization of surfaces, but its applicability has been limited in most cases at microscale spatial resolution, and the greatest challenge has been the scaling down to the nanoscale for fabrication and the use of nanometer-sized tips. Here, Pt nanoelectrodes with nanometer electroactive area were fabricated and employed for imaging a distribution of gold nanoparticles （AuNPs） and bioelectrocatalytic activity of a redox-active enzyme immobilized on gold surfaces.

Recognizing single phospholipid vesicle collisions on carbon fiber nanoelectrode

We recognize the stochastic collisions of dopamine contained phospholipid vesicle on carbon fiber nanoelectrode, extending the observation of discrete collision events on nanoelectrode to biologically relevant analytes. To decrease noise interference to the technique, the dimensions of nanoelectrode was systematically investigated and optimized. Scanning electron microscopy(SEM) further supported the comparable sizes of nanoelectrode and vesicles(~100 nm in diameter). Vesicles collision and rupture on the surface of nanoelectrode led to the dopamine release from vesicles, which could be electrochemically oxidized to dopamine-o-quinone and detected via voltammetry. The comparable size of the nanoelectrode with vesicles and fast voltammetry allowed differentiation of single collision events from the current magnitudes and peak widths in the electrochemical collision experiments, which shows the efficacy of the method to characterize vesicle samples. This work provides a foundation upon which quantitative sensor technology might be built for the detection of dopamine contained vesicles with high spatial and temporal resolution.

Development and Evaluation of Gold 3D Cylindrical Nanoelectrode Ensembles

Gold 3D cylindrical nanoelectrode ensembles （NEEs）, 100 nm in diameter and 500 nm in length were prepared by electroless template synthesis in polycarbonate filter membranes, followed by selective controlled chemical etching. The morphology of the nanowires and cylindrical NEEs was imaged by scanning electron microscopy. The protruding nanoelectrodes were in good parallel order. EDX study showed that the nanoelectrode elements consisted of pure gold. The electrochemical evaluation of the 3D electrodes was conducted using the well known [Fe（CN）6]^3-/[Fe（CN）6]^4- couple. Cyclic voltammgrams （CV） show a very low double layer charging current and a higher ratio of signal to background current than 2D disc NEEs. Electrochemical impedance spectroscopy （EIS） indicates that the 3D cylindrical NEEs effectively accelerate the charge transfer process, which is in consistent with the results of CV. The linear relationship with a slope of 0.5 between lg Ipc and lg v shows that linear diffusion is dominant on the 3D cylindrical NEEs at conventional scan rates.

Prolonged and highly efficient intracellular extraction of photosynthetic electrons from single algal cells by optimized nanoelectrode insertion

Harvesting photosynthetic electrons （PEs） from plant or algal cells can be a highly efficient and environmentally friendly way of generating renewable energy. Recent work on nanoelectrode insertion into algal cells has demonstrated the possibility to directly extract PEs from living algal cells with high efficiencies. However, the instability of the inserted cells limits the practicality of this technology. Here, the impact of nanoelectrode insertion on intracellular extraction of PEs is characterized with the goal of stabilizing algal cells after nanoelectrode insertion. Using nanoelectrodes 〈 500 nm in diameter, algal cells remained stable for over one week after insertion and continued to provide PEs through direct extraction by the inserted nanoelectrodes. After nanoelectrode insertion, a photosynthetic current density of 6 mA.cm-2, which is several fold higher than the current densities attained using approaches based on isolated thylakoid membranes or photosystem I complexes, was observed in the dark and during illumination at various light intensities.