Molecular electronics sensors on a scalable semiconductor chip: A platform for single-molecule measurement of binding kinetics and enzyme activity.

For nearly 50 years, the vision of using single molecules in circuits has been seen as providing the ultimate miniaturization of electronic chips. An advanced example of such a molecular electronics chip is presented here, with the important distinction that the molecular circuit elements play the role of general-purpose single-molecule sensors. The device consists of a semiconductor chip with a scalable array architecture. Each array element contains a synthetic molecular wire assembled to span nanoelectrodes in a current monitoring circuit. A central conjugation site is used to attach a single probe molecule that defines the target of the sensor. The chip digitizes the resulting picoamp-scale current-versus-time readout from each sensor element of the array at a rate of 1,000 frames per second. This provides detailed electrical signatures of the single-molecule interactions between the probe and targets present in a solution-phase test sample. This platform is used to measure the interaction kinetics of single molecules, without the use of labels, in a massively parallel fashion. To demonstrate broad applicability, examples are shown for probe molecule binding, including DNA oligos, aptamers, antibodies, and antigens, and the activity of enzymes relevant to diagnostics and sequencing, including a CRISPR/Cas enzyme binding a target DNA, and a DNA polymerase enzyme incorporating nucleotides as it copies a DNA template. All of these applications are accomplished with high sensitivity and resolution, on a manufacturable, scalable, all-electronic semiconductor chip device, thereby bringing the power of modern chips to these diverse areas of biosensing.

Adsorption of Nitrate and Phosphate on Basalt Based Nanostructured Zeolite 13X.

In this work, we prepared basalt based nanostructured zeolite 13X by alkali fusion and hydrothermal synthesis process. The sample prepared was characterized using XRD, SEM, and low-temperature nitrogen analysis. The adsorption equilibrium and kinetic characteristics of ammonia nitrogen (NH+4-N) and phosphate phosphorus (PO3-4-P) were investigated. It was found that the basalt based nanostructured zeolite 13X showed high adsorption capacities for NH+4-N (75 mg/g) and PO3-4-P (25 mg/g) under the experimental conditions used. Our results demonstrate that basalt based zeolite 13X can be a good alternative adsorbent for the simultaneously removal of NH+4-N and PO3-4-P from aqueous solution.

High-performance flexible hydrogen sensor made of WS2 nanosheet-Pd nanoparticle composite film.

We report a flexible hydrogen sensor, composed of WS2 nanosheet-Pd nanoparticle composite film, fabricated on a flexible polyimide substrate. The sensor offers the advantages of light-weight, mechanical durability, room temperature operation, and high sensitivity. The WS2-Pd composite film exhibits sensitivity (R 1/R 2, the ratio of the initial resistance to final resistance of the sensor) of 7.8 to 50,000 ppm hydrogen. Moreover, the WS2-Pd composite film distinctly outperforms the graphene-Pd composite, whose sensitivity is only 1.14. Furthermore, the ease of fabrication holds great potential for scalable and low-cost manufacturing of hydrogen sensors.

Correction: Dye adsorption mechanisms in TiO2 films, and their effects on the photodynamic and photovoltaic properties in dye-sensitized solar cells.

Correction for 'Dye adsorption mechanisms in TiO2 films, and their effects on the photodynamic and photovoltaic properties in dye-sensitized solar cells' by Kyung-Jun Hwang et al., Phys. Chem. Chem. Phys., 2015, 17, 21974-21981.

Enhanced Power Conversion Efficiency of Graphene/Silicon Heterojunction Solar Cells Through NiO Induced Doping.

We report a doping strategy, where nickel oxide (NiO) nanoparticle film coating is employed for graphene/Si heterojunction solar cells to improve the power conversion efficiency (PCE). NiO doping has been shown to improve the short circuit current (J(SC)) by 12%, open circuit voltage (V(OC)) by 25% and fill factor (FF) by 145% of the cells, in turn increasing the PCE from 1.37% to 4.91%. Furthermore, NiO doped graphene/Si solar cells don't show any significant performance degradation over 10 days revealing that NiO doping can be a promising approach for practical applications of graphene in solar cells.

Unusually High Optical Transparency in Hexagonal Nanopatterned Graphene with Enhanced Conductivity by Chemical Doping.

Graphene has received appreciable attention for its potential applications in flexible conducting film due to its exceptional optical, mechanical, and electrical properties. However increasing transmittance of graphene without sacrificing the electrical conductivity has been difficult. The fabrication of optically highly transparent (≈98%) graphene layer with a reasonable electrical conductivity is demonstrated here by nanopatterning and doping. Anodized aluminium oxide nanomask prepared by facile and simple self-assembly technique is utilized to produce an essentially hexagonally nanopatterned graphene. The electrical resistance of the graphene increases significantly by a factor of ≈15 by removal of substantial graphene regions via nanopatterning into hexagonal array pores. However, the use of chemical doping on the nanopatterned graphene almost completely recovers the lost electrical conductivity, thus leading to a desirably much more optically transparent conductor having ≈6.9 times reduced light blockage by graphene material without much loss of electrical conductivity. It is likely that the availability of large number of edges created in the nanopatterned graphene provides ideal sites for chemical dopant attachment, leading to a significant reduction of the sheet resistance. The results indicate that the nanopatterned graphene approach can be a promising route for simultaneously tuning the optical and electrical properties of graphene to make it more light-transmissible and suitable as a flexible transparent conductor.

Dye adsorption mechanisms in TiO2 films, and their effects on the photodynamic and photovoltaic properties in dye-sensitized solar cells.

The adsorption mechanism for the N719 dye on a TiO2 electrode was examined by the kinetic and diffusion models (pseudo-first order, pseudo-second order, and intra-particle diffusion models). Among these methods, the observed adsorption kinetics are well-described using the pseudo-second order model. Moreover, the film diffusion process was the main controlling step of adsorption, which was analysed using a diffusion-based model. The photodynamic properties in dye-sensitized solar cells (DSSCs) were investigated using time-resolved transient absorption techniques. The photodynamics of the oxidized N719 species were shown to be dependent on the adsorption time, and also the adsorbed concentration of N719. The photovoltaic parameters (Jsc, Voc, FF and η) of this DSSC were determined in terms of the dye adsorption amounts. The solar cell performance correlates significantly with charge recombination and dye regeneration dynamics, which are also affected by the dye adsorption amounts. Therefore, the photovoltaic performance of this DSSC can be interpreted in terms of the adsorption kinetics and the photodynamics of oxidized N719.

Palladium Decorated Graphene-Nanoribbon Network for Enhanced Gas Sensing.

The fabrication of large-scale graphene nanoribbon (GNR) network and its application for gas sensing are reported. A large area, nanoscale GNR network was produced by a facile approach of silver nanowires (Ag NWs) templated graphene masking and subsequent 02 plasma etching. GNR network shows significantly enhanced sensitivity to ammonia gas compared to pristine graphene layer. The gas detection sensitivity of the nanoscale GNR network is even further improved by decorating GNR network with palladium (Pd) or platinum (Pt) nanoparticles, which show a relative resistance response of 65% and 45%, respectively to 50 ppm (parts per million) of ammonia (NH3) in nitrogen (N2) at room temperature as well as good reversibility in air.

High-yielding and photolabile approaches to the covalent attachment of biomolecules to surfaces via hydrazone chemistry.

The development of strategies to couple biomolecules covalently to surfaces is necessary for constructing sensing arrays for biological and biomedical applications. One attractive conjugation reaction is hydrazone formation--the reaction of a hydrazine with an aldehyde or ketone--as both hydrazines and aldehydes/ketones are largely bioorthogonal, which makes this particular reaction suitable for conjugating biomolecules to a variety of substrates. We show that the mild reaction conditions afforded by hydrazone conjugation enable the conjugation of DNA and proteins to the substrate surface in significantly higher yields than can be achieved with traditional bioconjugation techniques, such as maleimide chemistry. Next, we designed and synthesized a photocaged aryl ketone that can be conjugated to a surface and photochemically activated to provide a suitable partner for subsequent hydrazone formation between the surface-anchored ketone and DNA- or protein-hydrazines. Finally, we exploit the latent functionality of the photocaged ketone and pattern multiple biomolecules on the same substrate, effectively demonstrating a strategy for designing substrates with well-defined domains of different biomolecules. We expect that this approach can be extended to the production of multiplexed assays by using an appropriate mask with sequential photoexposure and biomolecule conjugation steps.

Tailoring n-ZnO/p-Si branched nanowire heterostructures for selective photoelectrochemical water oxidation or reduction.

We report the fabrication of three-dimensional (3D) branched nanowire (NW) heterostructures, consisting of periodically ordered vertical Si NW trunks and ZnO NW branches, and their application for solar water splitting. The branched NW photoelectrodes show orders of magnitudes higher photocurrent compared to the bare Si NW electrodes. More interestingly, selective photoelectrochemical cathodic or anodic behavior resulting in either solar water oxidation or reduction was achieved by tuning the doping concentration of the p-type Si NW core. Specifically, n-ZnO/p-Si branched NW array electrodes with lightly doped core show broadband absorption from UV to near IR region and photocathodic water reduction, while n-ZnO/p(+)-Si branched NW arrays show photoanodic water oxidation with photoresponse only to UV light. The photoelectrochemical stability for over 24 h under constant light illumination and fixed biasing potential was achieved by coating the branched NW array with thin layers of TiO2 and Pt. These studies not only reveal the promise of 3D branched NW photoelectrodes for high efficiency solar energy harvesting and conversion to clean chemical fuels, but also developing understanding enabling rational design of high efficiency robust photocathodes and photoanodes from low-cost and earth-abundant materials allowing practical applications in clean renewable energy.

Magnetically guided nano-micro shaping and slicing of silicon.

Silicon is one of the most important materials for modern electronics, telecom, and photovoltaic (PV) solar cells. With the rapidly expanding use of Si in the global economy, it would be highly desirable to reduce the overall use of Si material, especially to make the PVs more affordable and widely used as a renewable energy source. Here we report the first successful direction-guided, nano/microshaping of silicon, the intended direction of which is dictated by an applied magnetic field. Micrometer thin, massively parallel silicon sheets, very tall Si microneedles, zigzag bent Si nanowires, and tunnel drilling into Si substrates have all been demonstrated. The technique, utilizing narrow array of Au/Fe/Au trilayer etch lines, is particularly effective in producing only micrometer-thick Si sheets by rapid and inexpensive means with only 5 µm level slicing loss of Si material, thus practically eliminating the waste (and also the use) of Si material compared to the ~200 µm kerf loss per slicing and ~200 µm thick wafer in the typical saw-cut Si solar cell preparation. We expect that such nano/microshaping will enable a whole new family of novel Si geometries and exciting applications, including flexible Si circuits and highly antireflective zigzag nanowire coatings.

A Scalable CMOS Molecular Electronics Chip for Single-Molecule Biosensing.

This work reports the first CMOS molecular electronics chip. It is configured as a biosensor, where the primary sensing element is a single molecule "molecular wire" consisting of a ∼100 GΩ, 25 nm long alpha-helical peptide integrated into a current monitoring circuit. The engineered peptide contains a central conjugation site for attachment of various probe molecules, such as DNA, proteins, enzymes, or antibodies, which program the biosensor to detect interactions with a specific target molecule. The current through the molecular wire under a dc applied voltage is monitored with millisecond temporal resolution. The detected signals are millisecond-scale, picoampere current pulses generated by each transient probe-target molecular interaction. Implemented in a 0.18 µm CMOS technology, 16k sensors are arrayed with a 20 µm pitch and read out at a 1 kHz frame rate. The resulting biosensor chip provides direct, real-time observation of the single-molecule interaction kinetics, unlike classical biosensors that measure ensemble averages of such events. This molecular electronics chip provides a platform for putting molecular biosensing "on-chip" to bring the power of semiconductor chips to diverse applications in biological research, diagnostics, sequencing, proteomics, drug discovery, and environmental monitoring.

Extreme superomniphobicity of multiwalled 8 nm TiO2 nanotubes.

We report unprecedented superomniphobic characteristics of nanotube-structured TiO(2) surface fabricated by electrochemical etching and hydrothermal synthesis process, with the wettability contact angles for water and oil both being ∼174° or higher. A tangled forest of ∼8-nm-diameter, multiwalled nanotubes of TiO(2) was produced on the microtextured Ti surface, with the overall nanotube length controlled to 150 nm by adjusting the processing time. Wettability measurements indicate that the nanotube surface is extremely nonwettable to both water and oil. The contact angle of the 8 nm TiO(2) nanotube surface after perfluorosilane coating is extremely high (178°) for water droplets indicating superhydrophobic properties. The contact angle for oil, measured using a glycerol droplet, is also very high, about 174°, indicating superoleophobic characteristics. These dual nonwetting properties, superomniphobic characteristics, are in sharp contrast to the as-made TiO(2) nanotubes which exhibit superhydrophilic properties with a contact angle of essentially ∼0°. Such an extreme superomniphobic material made by a simple and versatile method can be useful for a variety of technical applications. It is interesting to note that all three properties can be obtained with identical nanotube structures. A nanometer-scaled structure introduced by hydrothermally grown TiO(2) nanotubes is an effective air trapping nanostructure in enhancing the amphiphobic (superomniphobic) wettability.

Antibiofouling, sustained antibiotic release by Si nanowire templates.

Loading or filling nanostructures with antibiotics can be one of the relevant approaches for obtaining a controlled drug release rate. Vertically aligned silicon nanowire (SiNW) arrays with 10-40 nm diameter wires having 1-3 microm in length obtained by the electroless etching (EE) technique are used in this study as novel nanostructures for mediating drug delivery. Here we report controlled antibiotic activity and sustained bioavailability from SiNW arrays and also show microstructural manipulations for a tunable release rate. As well, we have demonstrated biodegradability of SiNWs in phosphate buffer saline (PBS) solution. Strikingly suppressed cell and protein adhesion was observed on our SiNW surface, which indicates a reduced probability for biofouling and drug release impediments. Such antibiotic release from the nanowire-structured surface can provide more reliable antibiotic protection at a targeted implantation or biosensor site.

Geometry transformation and alterations of periodically patterned Si nanotemplates by dry oxidation.

We report on the size-dependent transformation and geometrical modifications of periodically patterned Si templates by a combination of dry oxidation and chemical etching. Deep ultraviolet lithography patterned circular holes with diameters varying between 190 nm and 1 microm on Si wafers were oxidized at 1000 degrees C using dry oxygen for various durations, with selected samples chemically etched for oxide removal for additional alterations. An interesting phenomenon of a circular-to-square shape transformation of the holes was observed, which was particularly pronounced in the sub-200 nm regime. We tentatively attribute the change to the surface energy and geometry constraints in nanoscale patterns.

Synthesis of zeolitic material from basalt rock and its adsorption properties for carbon dioxide.

A zeolitic 4A type material was successfully prepared from natural basalt rock by applying an alkali fusion process and hydrothermal synthesis. In particular, the optimum synthetic conditions were examined at different crystallization times. Several methods such as XRD, SEM, EDX, and N2 and CO2 adsorption analysis were used to characterize the synthesized 4A type zeolite. In addition, CO2 adsorption equilibrium capacities for this basalt base zeolite were measured over temperature ranges from 283 to 303 K and pressure ranges from 0.1 to 1500 kPa in a volumetric adsorption apparatus. Then the results were compared to those of commercial zeolite. Moreover, to further investigate the surface energetic heterogeneity of the prepared zeolite, the isosteric heat of adsorption and adsorption energy distribution was determined. We found that basalt based zeolite 4A shows a CO2 adsorption equilibrium capacity of 5.9 mmol g-1 (at 293 K and 1500 kPa) which is much higher than the 3.6 mmol g-1 of the commercial zeolite as its micro-pore surface area, micro-pore volume and surface heterogeneity indicate.

Matrix Topographical Cue-Mediated Myogenic Differentiation of Human Embryonic Stem Cell Derivatives.

Biomaterials varying in physical properties, chemical composition and biofunctionalities can be used as powerful tools to regulate skeletal muscle-specific cellular behaviors, including myogenic differentiation of progenitor cells. Biomaterials with defined topographical cues (e.g., patterned substrates) can mediate cellular alignment of progenitor cells and improve myogenic differentiation. In this study, we employed soft lithography techniques to create substrates with microtopographical cues and used these substrates to study the effect of matrix topographical cues on myogenic differentiation of human embryonic stem cell (hESC)-derived mesodermal progenitor cells expressing platelet-derived growth factor receptor alpha (PDGFRA). Our results show that the majority (>80%) of PDGFRA+ cells on micropatterned polydimethylsiloxane (PDMS) substrates were aligned along the direction of the microgrooves and underwent robust myogenic differentiation compared to those on non-patterned surfaces. Matrix topography-mediated alignment of the mononucleated cells promoted their fusion resulting in mainly (~86%⁻93%) multinucleated myotube formation. Furthermore, when implanted, the cells on the micropatterned substrates showed enhanced in vivo survival (>5⁻7 times) and engraftment (>4⁻6 times) in cardiotoxin-injured tibialis anterior (TA) muscles of NOD/SCID mice compared to cells cultured on corresponding non-patterned substrates.

MoS2 Nanosheet-Pd Nanoparticle Composite for Highly Sensitive Room Temperature Detection of Hydrogen.

Highly sensitive hydrogen detection at room temperature can be realized by employing solution-processed MoS2 nanosheet-Pd nanoparticle composite. A MoS2-Pd composite exhibits greater sensing performance than its graphene counterpart, indicating that solvent exfoliated MoS2 holds great promise for inexpensive and scalable fabrication of highly sensitive chemical sensors.

3D Branched nanowire photoelectrochemical electrodes for efficient solar water splitting.

We report the systematic study of 3D ZnO/Si branched nanowire (b-NW) photoelectrodes and their application in solar water splitting. We focus our study on the correlation between the electrode design and structures (including Si NW doping, dimension of the trunk Si and branch ZnO NWs, and b-NW pitch size) and their photoelectrochemical (PEC) performances (efficiency and stability) under neutral conditions. Specifically, we show that for b-NW electrodes with lightly doped p-Si NW core, larger ZnO NW branches and longer Si NW cores give a higher photocathodic current, while for b-NWs with heavily doped p-Si NW trunks smaller ZnO NWs and shorter Si NWs provide a higher photoanodic current. Interestingly, the photocurrent turn-on potential decreases with longer p-Si NW trunks and larger ZnO NW branches resulting in a significant photocathodic turn-on potential shift of ~600 mV for the optimized ZnO/p-Si b-NWs compared to that of the bare p-Si NWs. A photocathode energy conversion efficiency of greater than 2% at -1 V versus Pt counter electrode and in neutral solution is achieved for the optimized ZnO/p-Si b-NW electrodes. The PEC performances or incident photon-to-current efficiency are further improved using Si NW cores with smaller pitch size. The photoelectrode stability is dramatically improved by coating a thin TiO2 protection layer using atomic-layer deposition method. These results provide very useful guidelines in designing photoelectrodes for selective solar water oxidation/reduction and overall spontaneous solar fuel generation using low cost earth-abundant materials for practical clean solar fuel production.

Enhanced Raman signals from switchable nanoparticle probes.

We demonstrate here a DNA-based conformationally switchable nanodumbell structure that modulates the interparticle distance between two gold-silver core-shell nanoparticles to induce significant changes in the SERS signal.