Do-It-Yourself Pyramidal Mold for Nanotechnology.

The handcrafted fabrication of a pyramidal mold on a silicon wafer for nanopatterning was investigated. This process started with the manual delivery of an aqueous glycerol solution onto the SiO2/Si wafer using a micropipette and subsequent drying to form a hemisphere whose diameter is in the range of hundreds of micrometers. A coating of polystyrene (PS) onto this wafer generates a circular hole caused by dewetting. Subsequently, anisotropic wet-etching with the PS film as a mask produces a pyramidal trench, whose apex approaches hundreds of nanometers. Various elastomeric materials were casted into this pyramidal mold. A pyramidal tip mounted on a simple micropositioner was used for electrochemistry and patterning of a protein. First, an agarose hydrogel was cast with a hydrogel pen for the electrochemical reaction (HYPER). The redox reaction at the HYPER-electrode interface demonstrated the characteristics of an ultramicroelectrode or bulk electrode based on the contact area. Second, the pyramidal polydimethylsiloxane served as a polymer pen for the contact printing of silane on a glass substrate. After the successive immobilization of biotin and avidin with fluorescence labeling, the resulting fluorescence image demonstrated the successful patterning of the protein. This new process for the creation of a pyramidal mold, referred to as a "do-it-yourself" process, offers advantages to nonspecialists in nanotechnology compared to conventional lithography, specifically simplicity, rapidity, and low cost.

Can Static Electricity on a Conductor Drive a Redox Reaction: Contact Electrification of Au by Polydimethylsiloxane, Charge Inversion in Water, and Redox Reaction.

We investigated the static charge generation by contact electrification between Au and polydimethylsiloxane (PDMS) and the redox reaction by the static charge in the aqueous phase, to reveal the mechanism of contact electrification and redox reaction which may be applied to mechanical-to-chemical energy harvesting. First, the static charge distribution on the equipotential Au was probed through Kelvin probe force microscopy (KPFM) in air after the contact with patterned PDMS. Positive charges are localized on the contact areas indicating the ion migration while the polarity becomes negative after water contact. Second, the redox reaction by the charged Au was electrochemically monitored using open circuit potential (OCP), stripping voltammetry, and copper underpotential deposition (UPD). All electrochemical experiments consistently resulted in the reduction of the reactant by the charged Au within the highly dielectric water media. We concluded that the reduction is not driven by the discharge of static charge on Au but by reducing radicals.

A wet-chemistry-based hydrogel sensing platform for 2D imaging of pressure, chemicals and temperature.

Human skin can perceive pressure, chemical compounds and temperature with a high spatial resolution via specific receptors. Inspired by human skin, we present a wet-chemistry based hydrogel sensing platform for 2D imaging sensitive to specific external stimuli, e.g., pressure, chemicals and temperature. This platform is composed of a hydrogel pyramidal array on a single electrode. Each pyramid serves as a spatially separated reservoir for chemical reactions, enabling independent pixels for sensing without individual electrodes. Depending on the electrochemiluminescence (ECL) electrolyte for specific stimuli, our platform possesses 2D imaging capabilities with high sensitivity for pH and temperature in addition to pressure via the deformation of the viscoelastic hydrogel. This work represents an important step toward the application of sensitive chemical reactions for various external stimuli to biocompatible electronic skins based on hydrogels without addressing circuit for each pixel.

Programmable Electrochemical Rectifier Based on a Thin-Layer Cell.

A programmable electrochemical rectifier based on thin-layer electrochemistry is described here. Both the rectification ratio and the response time of the device are programmable by controlling the gap distance of the thin-layer electrochemical cell, which is easily controlled using commercially available beads. One of the electrodes was modified using a ferrocene-terminated self-assembled monolayer to offer unidirectional charge transfers via soluble redox species. The thin-layer configuration provided enhanced mass transport, which was determined by the gap thickness. The device with the smallest gap thickness (∼4 µm) showed an unprecedented, high rectification ratio (up to 160) with a fast response time in a two-terminal configuration using conventional electronics.

H(+)-Assisted fluorescent differentiation of Cu(+) and Cu(2+): effect of Al(3+)-induced acidity on chemical sensing and generation of two novel and independent logic gating pathways.

A novel Schiff base probe exhibited strong 'turn-ON' fluorescence for Cu(2+) at 345 nm, Al(3+) at 445 nm, and Cu(+) at 360 nm in the presence of Al(3+) in organic solvent (acetonitrile), which allowed for construction of molecular logic gates 'INH' and '1:2 DEMULTIPLEXING.' H(+) generated from Al(3+) contributed greatly to Cu(+) chemosensing based on a redox non-innocence mechanism.

A hydrogel pen for electrochemical reaction and its applications for 3D printing.

A hydrogel pen consisting of a microscopic pyramid containing an electrolyte offers a localized electroactive area on the nanometer scale via controlled contact of the apex with a working electrode. The hydrogel pen merges the fine control of atomic force microscopy with non-linear diffusion of an ultramicroelectrode, producing a faradaic current that depends on the small electroactive area. The theoretical and experimental investigations of the mass transport behavior within the hydrogel reveal that the steady-state current from the faradaic reaction is linearly proportional to the deformed length of the hydrogel pen by contact, i.e. signal transduction of deformation to an electrochemical signal, which enables the fine control of the electroactive area in the nanometer-scale regime. Combined with electrodeposition, localized electrochemistry of the hydrogel pen results in the ability to fabricate small sizes (110 nm in diameter), tall heights (up to 30 µm), and arbitrary structures, thereby indicating an additive process in 3 dimensions by localized electrodeposition.

Subcellular neural probes from single-crystal gold nanowires.

Size reduction of neural electrodes is essential for improving the functionality of neuroprosthetic devices, developing potent therapies for neurological and neurodegenerative diseases, and long-term brain­computer interfaces. Typical neural electrodes are micromanufactured devices with dimensions ranging from tens to hundreds of micrometers. Their further miniaturization is necessary to reduce local tissue damage and chronic immunological reactions of the brain. Here we report the neural electrode with subcellular dimensions based on single-crystalline gold nanowires (NWs) with a diameter of ∼100 nm. Unique mechanical and electrical properties of defect-free gold NWs enabled their implantation and recording of single neuron-activities in a live mouse brain despite a ∼50× reduction of the size compared to the closest analogues. Reduction of electrode dimensions enabled recording of neural activity with improved spatial resolution and differentiation of brain activity in response to different social situations for mice. The successful localization of the epileptic seizure center was also achieved using a multielectrode probe as a demonstration of the diagnostics potential of NW electrodes. This study demonstrated the realism of single-neuron recording using subcellular-sized electrodes that may be considered a pivotal point for use in diverse studies of chronic brain diseases.

Enhanced adhesion of preosteoblasts inside 3D PCL scaffolds by polydopamine coating and mineralization.

In tissue engineering, fabrication of 3D scaffolds with well-defined, inter-connected pores followed by culture of mammalian cells is a typical approach. In practice, however, hydrophobicity of scaffold surfaces is not suitable for cells to be adhered because of poor wettability. Especially, infiltration followed by adhesion of cells inside hydrophobic scaffolds remains as a challenge. Thus, hydrophilic conversions of the surfaces regardless of surface location are critical for success. Herein, a method to enhance infiltration and adhesion of preosteoblasts inside hydrophobic poly(ϵ-caprolactone) (PCL) scaffolds by a bio-inspired, hydroxyapatite formation is demonstrated. The approach can be a general method for controlling hydrophilicity of inner surfaces of scaffolds.

Synthesis of gold coated magnetic microparticles and their application for electrochemical glucose sensing by the enzymatically precipitated prussian blue.

An enzyme stimulated deposition of prussian blue onto the gold-coated magnetic microparticles is described. We propose to synthesize the continuous outer gold layer on the magnetic particle for a gold working electrode and its superparamagnetic property. In-depth characterization of the gold shell formation was studied with scanning electron microscopy, energy-dispersive X-ray spectroscopy, cyclic voltammetry. The gold-coated magnetic microparticles offered adhesive layer for the immobilization of glucose oxidase catalyzing the generation of prussian blue in the presence of glucose. The assembled prussian blue on the gold shell surfaces was detected with electrochemical measurements depending on the glucose concentration. With accomplishing the linear response range from 0.2 mM to 10 mM of glucose, this approach successfully proposed the applicability of the magnetic core-gold shell structures to the electrochemical bioassay area.

Synthetic, 119Sn NMR spectroscopic, electrochemical, and reactivity study of organotin A3 corrolates including chiral and ferrocenyl derivatives.

Various R/Ar-functionalized tin 5,10,15-tris(pentafluorophenyl)corrolate derivatives are reported herein including the first ferrocenyltin corrolate species. The isopropyl, sec-butyl-, 2-methyl-n-butyl-, phenyl-, 2-thienyl-, and ferrocenyltin species have been prepared and characterized through (1)H, (13)C, and (119)Sn HMQC NMR spectroscopy, mass spectrometry, UV-vis and photoluminescent spectroscopy, and cyclic voltammetry studies. J(C/H-Sn) NMR spectroscopic couplings and ring-current effects (upfield shifting) were determined for the R-Sn axial hydrogen and carbon atoms. This report adds to older conceptually similar reports, by, i.e., Janson et al. (J. Am. Chem. Soc. 1969, 91, 5210) and Walker et al. (J. Am. Chem. Soc.1983, 105, 6923-6929), as discussed herein. Such NMR spectroscopic aspects are discussed for these model systems. Compound Sn-Ph bond cleavage was achieved by treatment with I(2).

Electrochemical detection of biomolecule with mixed self-assembled monolayers of ferrocene-undecanethiol.

Thiol self-assembled monolayers (SAMs) have been widely used as a modification method to immobilize biomolecules to gold surfaces. However, the additional layers of SAM and biomolecules make electron transfer difficult, leading to a large overpotential in electrical signal. Electron transfer mediation is the most popular solution to overcome the problem of the overpotential for an electrochemical biosensor. We introduced mixed SAMs of mercapto-dodecanoic acid (MDA) and ferrocene-undecanthiol. Ferrocene-undecanthiol acts as an electron transfer mediator and MDA is used for immobilization of biomolecule. The electron transferability of mixed SAMs is affected by pH, kinds of electrolytes, and the composition of the thiol molecule. We optimized the carboxyl acid and ferrocene molecule ratio which is a crucial factor in the performance of mixed SAMs and electrochemically detected the avidin. The detection limit was 2.0 microg/mL of avidin concentration.

Aptamer based electrochemical sensor system for protein using the generation/collection mode of scanning electrochemical microscope (SECM).

To detect the target molecules, aptamers are currently focused on and the use of aptamers for biosensing is particularly interesting, as aptamers could substitute antibodies in bioanalytical sensing. So this paper describes the novel electrochemical system for protein in sandwich manner by using the aptamers and the scanning electrochemical microscope (SECM). For protein detection, sandwich system is ideal since labeling of the target protein is not necessary. To develop the electrochemical protein sensor system, thrombin was chosen as a target protein since many aptamers for it were already reported and two different aptamers, which recognize different positions of thrombin, were chosen to construct sandwich type sensing system. In order to obtain the electrochemical signal, the glucose oxidase (GOD) used for labeling the detection aptamers since it has large amount of stability in aqueous solution. One aptamer was immobilized onto the gold electrode and the other aptamer for detection was labeled with GOD for generation of the electric signal. Thrombin was detected in sandwich manner with aptamer immobilized onto the gold electrode and the GOD labeled aptamer. The enzymatic signal, generated from glucose addition after the formation of the complex of thrombin, was measured. The generation-collection mode of SECM was used for amperometric H2O2 detection.

Ordered polymeric microhole array made by selective wetting and applications for electrochemical microelectrode array.

In this paper, we report the microelectrode array fabrication using selective wetting/dewetting of polymers on a chemical pattern which is a simple and convenient method capable of creating negative polymeric replicas using polyethylene glycol (PEG) as a clean and nontoxic sacrificial layer. The fabricated hole-patterned polypropylene film on gold demonstrated enhanced electrochemical properties. The chemical pattern is fabricated by microcontact printing using octadecanethiol (ODT) as an ink on gold substrate. When PEG is spin-cast on the chemical pattern, PEG solution selectively dewets the ODT patterned areas and wets the remaining bare gold areas, leading to the formation of arrayed PEG dots. A negative replicas of the PEG dot array is obtained by spin-coating of polypropylene (PP) solution in hexane which preferentially interacts with the hydrophobic ODT region on the patterned gold surface. The arrayed PEG dots are not affected the during PP spin-coating step because of their intrinsic immiscibility. Consequently, the hole-patterned PP film is obtained after PEG removal. The electrochemical signal of the PP film demonstrates the negligible leakage current by high dielectric and self-healing of defects on the chemical pattern by the polymer. This method is applicable to fabrication of microelectrode arrays and possibly can be employed to fabricate a variety of functional polymeric structures, such as photomasks, arrays of biomolecules, cell arrays, and arrays of nanomaterials.

Nanosieving of anions and cavity-size-dependent association of cyclodextrins on a 1-adamantanethiol self-assembled monolayer.

In this paper, we studied charge transfer through a self-assembled monolayer (SAM) of 1-adamantanethiol on gold. Charge transfer through the 1-adamantanethiol SAM depended on the type of anion present when [Fe(CN)6]3- was used as a redox probe. The sluggish charge transfer process was monitored by cyclic voltammetry using the relatively large and hydrophobic perchlorate and hexafluorophosphate ions as the supporting electrolyte. In contrast, the charge transfer kinetics were nearly identical to those measured on bare gold with chloride, sulfate, and nitrate ions as the supporting electrolyte. We investigated the adsorption of alpha- and beta-cyclodextrin on the 1-adamantanethiol SAM via a host-guest interaction. The 1-adamantanethiol SAM could not bind beta-cyclodextrin via a host-guest interaction, probably due to the proximity of neighboring adamantine molecules on the surface. Immobilization of alpha-cyclodextrin by formation of an exterior complex with the SAM suppressed charge transfer. The adsorbed alpha-cyclodextrin was quantified using faradaic impedance experiments. The obtained adsorption isotherm was in good agreement with the Langmuir isotherm with a binding constant of 39.53 M(-1).

Synthetic, cyclic voltammetric, structural, EPR, and UV-Vis spectroscopic studies of thienyl-containing meso-A(2)B-cor(Cr(V)=O) systems: consideration of three interrelated molecular detection modalities.

We report eight new A(2)B-type (M(n+)) corrolate compounds (two structural studies) that include the oxo[5,15-bis(pentafluorophenyl)-10-R-corrolatochromium(V)] [R = 2-/3-thienyl (1a/2a), 3-thianaphthyl (3a)] species. The first examples of meso-A(2) (thienyl)- and Cr-A(2)B-corrole types are represented herein. Characterization includes cyclic voltammetry, electron paramagnetic resonance, 2D ((1)H and (13)C) NMR, and UV-vis spectroscopy, mass spectrometry, and elemental analysis. Compounds 1a-3a have enabled analyte binding capacity studies. [Cu(2+)...O=Cr(cor)] binding represents a new selective mode of corrole-based detection, whereas free-base A(2)B-corroles exhibited limited M(n+) selectivity. The 10-position substitution affects optical profiles in analyte titrations. A limited amount of PPh(3) O-atom uptake from [O=Cr(cor)] was also demonstrated.

An electrochemical immunosensor using p-aminophenol redox cycling by NADH on a self-assembled monolayer and ferrocene-modified Au electrodes.

Redox cycling of enzymatically amplified electroactive species has been widely employed for high signal amplification in electrochemical biosensors. However, gold (Au) electrodes are not generally suitable for redox cycling using a reducing (or oxidizing) agent because of the high background current caused by the redox reaction of the agent at highly electrocatalytic Au electrodes. Here we report a new redox cycling scheme, using nicotinamide adenine dinucleotide (NADH), which can be applied to Au electrodes. Importantly, p-aminophenol (AP) redox cycling by NADH is achieved in the absence of diaphorase enzyme. The Au electrodes are modified with a mixed self-assembled monolayer of mercaptododecanoic acid and mercaptoundecanol, and a partially ferrocenyl-tethered dendrimer layer. The self-assembled monolayer of long thiol molecules significantly decreases the background current of the modified Au electrodes, and the ferrocene modification facilitates easy oxidation of AP. The low amount of ferrocene on the Au electrodes minimizes ferrocene-mediated oxidation of NADH. In sandwich-type electrochemical immunosensors for mouse immunoglobulin G (IgG), an alkaline phosphatase label converts p-aminophenylphosphate (APP) into electroactive AP. The amplified AP is oxidized to p-quinoneimine (QI) by electrochemically generated ferrocenium ion. NADH reduces QI back to AP, which can be re-oxidized. This redox cycling enables a low detection limit for mouse IgG (1 pg mL(-1)) to be obtained.

Label-free aptasensor for platelet-derived growth factor (PDGF) protein.

A label-free aptasensor for platelet-derived growth factor (PDGF) protein is reported. The aptasensor uses mixed self-assembled monolayers (SAMs) composed of a thiol-modified PDGF binding aptamer and 6-mercaptohexanol (MCH) on a gold electrode. The SAMs were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV) before and after binding of the protein using [Fe(CN)(6)](3-/4-), a redox marker ion as an indicator for the formation of a protein-aptamer complex. The CVs at the PDGF modified electrode showed significant differences, such as changes in the peak currents and peak-to-peak separation, before and after binding of the target protein. The EIS spectra, in the form of Nyquist plots, were analyzed with a Randles circuit while the electron transfer resistance R(ct) was used to monitor the binding of the target protein. The results showed that, without any modification to the aptamer, the target protein can be recognized effectively at the PDGF binding aptamer SAMs at the electrode surface. Control experiments using non-binding oligonucleotides assembled at the electrode surfaces also confirmed the results and showed that there was no formation of an aptamer-protein complex. The DPV signal at the aptamer functionalized electrode showed a linearly decreased marker ion peak current in a protein concentrations range of 1-40 nM. Thus, label-free detection of PDGF protein at an aptamer modified electrode has been demonstrated.

Characterization and electrocatalytic properties of Prussian blue electrochemically deposited on nano-Au/PAMAM dendrimer-modified gold electrode.

Gold electrode was modified with 3-mercaptopropionic acid (MPA) and further reacted with poly(amidoamine) (PAMAM) dendrimer (generation 4.0) then attached the nano-Au to obtain films on which Prussian blue (PB) was electrochemically deposited to afford much wider pH adaptive range, much better electrochemical stability and excellent electrochemical response. The microstructure and electrochemical behavior of Au/MPA/PAMAM/nano-Au/PB electrode were investigated by scanning electron microscopy (SEM) and cyclic voltammetry. The electrochemical response of the Au/MPA/PAMAM/nano-Au/PB-modified electrode for the electrocatalytic reduction of hydrogen peroxide was investigated, and it was found that the sensitivity as well as the corresponding detection limits were improved as compared to the voltammetric response of a Au/PB-modified electrode and Au/MPA/PAMAM/PB electrode. Based on this, a new electrochemical sensor for determination of hydrogen peroxide has been developed.

Protein micropatterning based on electrochemically switched immobilization of bioligand on electropolymerized film of a dually electroactive monomer.

We demonstrate a protein micropatterning method based on electropolymerization of a monomer with two electroactive units, hydroquinone monoester and disulfide, which enables electrochemical ON-OFF switching for immobilization of bioligands on electrodes modified with the electropolymerized film.

Sieving behaviour of nanoscopic pores by hydrated ions.

In this study, for the first time, the anion dependency of Ag-deposition on self-assembled monolayers (SAMs) with alkyl chains long enough to meet the densely packed and well-organized surface is reported. Irrespective of pH, types of terminal groups of the SAMs, and the convective mass transfer condition, SAM structures show the "sieving behaviour" to the Ag deposition by the composition of the electrolytes.