Electrostatic control of lipid bilayer self-spreading using a nanogap gate on a solid support.

We have demonstrated for the first time that the self-spreading of supported lipid bilayers can be controlled by the temporal switching of an electric field applied between nanogap electrodes. To account for this phenomenon, we propose an electrostatic trapping model in which an electric double layer plays an important role. The validity of this mechanism was verified by the dependence of self-spreading on the nanogap width and the ionic concentration of the electrolyte. Our results provide a promising tool for the temporal and spatial control of lipid bilayer formation for nanobio devices.

Supported lipid bilayer composition microarray fabricated by pattern-guided self-spreading.

We report on the fabrication of a microarray of supported lipid bilayers (SLBs) with different chemical compositions and demonstrate its biosensing application. The technique utilizes the phenomenon of lipid self-spreading on a patterned surface, which offers complete positional selectivity for a supported lipid bilayer. We describe the fabrication of parallel 10-µm-wide lines, each filled with an SLB with a unique composition, at 5 µm intervals. Structures obtained with our new technique are finer and more highly integrated than previously reported structures that employ the vesicle fusion technique on patterned surfaces. We also detected specific binding between biotin and streptavidin with high contrast, indicating that the microarray is valuable for biosensing applications.

Pattern formation and molecular transport of histidine-tagged GFPs using supported lipid bilayers.

We fabricated a heterogeneous supported lipid bilayer (SLB) by employing binary lipid mixtures comprising a saturated acyl chain DSPC and an unsaturated acyl chain nickel-chelating lipid. By using the specific adsorption properties of histidine-tagged proteins (His-tagged GFPs) in relation to nickel-chelating lipids, we demonstrated protein pattern formation on the SLB corresponding to the phase separation pattern of the SLB. In addition, by using a lipid mixture consisting of an unsaturated acyl chain DOPC and a nickel-chelating lipid, and His-tagged GFPs, we succeeded in transporting the proteins along a hydrophilic micropattern on a SiO(2) substrate. The protein transport is induced by the self-spreading behavior of a fluid SLB with a kinetic spreading coefficient beta = 10.4 microm(2) s(-1). This method provides a guide for strategically carrying various biomolecules to specific positions by using a soft biointerface on a solid surface. In addition, the results demonstrate the importance of using techniques that allow the controlled manipulation of biomolecules based on the static or dynamic properties of the SLB platform.

Anisotropic assembly of gold nanorods assisted by selective ion recognition of surface-anchored crown ether derivatives.

Gold nanorods (NRs) mixed with crown ether derivatives exhibited the efficient and selective recognition of Na+ and K+ ions, which were detected by localized surface plasmon absorption in response to dispersed and aggregated gold NRs. Furthermore, in the aggregates preferential end-to-end or side-to-side assembly of NRs was observed which was dependent on the additive concentration.

A new morphology of copper 7,7,8,8-tetracyano-p-quinodimethane.

Morphology control is a long-standing problem that needs to be solved for making the switching mechanism of copper 7,7,8,8-tetracyano-p-quinodimethane (CuTCNQ) understood all the time, but up till now how many morphologies CuTCNQ possesses and which morphology should be responsible for the on/off switching phenomenon are still unclear. A new morphology of CuTCNQ, namely the tubular structure, has been obtained and characterized in our experiment, whose formation mechanism has also been investigated. Through characterizing, we can conclude that the tubular structure belongs to the phase I, which can be further confirmed by the electrical measurements. From the I-V plots, the carrier mobility of the tubular structure is estimated to be approximately 0.1 cm2 V-1 s-1, which suggests the potential application of CuTCNQ in devices.

Self-propelled ion gel at air-water interface.

We report on a self-propelled gel using ionic liquid as a new type of self-propellant that generates a powerful and durable motion at an air-water interface. The gel is composed of 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMIM-TFSI) and poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-co-HFP)). A long rectangular ion gel piece placed on the interface shows rapid rotation motion with maximum frequency close to 10 Hz, corresponding to the velocity over 300 mms-1 at an outmost end of the piece. The rotation continues for ca. 102 s, followed by a reciprocating motion (<~103 s) and a nonlinear motion in long-time observations (>~103 s). The behaviours can be explained by the model considering elution of EMIM-TFSI to the air-water interface, rapid dissolution into water, and slow diffusion in an inhomogeneous polymer gel network. Because the self-propellants are promptly removed from the interface by dissolution, durable self-propelled motions are observed also at limited interface areas close in size to the gel pieces. A variety of motions are induced in such systems where the degree of freedom in motion is limited. As the ion gel possesses formability and processability, it is also advantageous for practical applications. We demonstrate that the gel does work as an engine.

Microchannel device using self-spreading lipid bilayer as molecule carrier.

We propose a microchannel device that employs a surface-supported self-spreading lipid bilayer membrane as a molecule carrying medium. The device has a micropattern structure fabricated on a SiO2 surface by photolithography, into which a self-spreading lipid bilayer membrane is introduced as the carrier medium. This system corresponds to a microchannel with a single lipid bilayer membrane height of approximately 5 nm, compared with conventional micro-fluidic channels that have a section height and width of at least several microm. The device is beneficial for detecting intermolecular interactions when molecules carried by the self-spreading lipid bilayer collide with each other in the microchannel. The validity of the device was confirmed by observing the fluorescence resonance energy transfer (FRET) between two dye molecules, coumarin and fluorescein.

Energy Dissipation in Graphene Mechanical Resonators with and without Free Edges.

Graphene-based nanoelectromechanical systems (NEMS) have high future potential to realize sensitive mass and force sensors owing to graphene's low mass density and exceptional mechanical properties. One of the important remaining issues in this field is how to achieve mechanical resonators with a high quality factor (Q). Energy dissipation in resonators decreases Q, and suppressing it is the key to realizing sensitive sensors. In this article, we review our recent work on energy dissipation in doubly-clamped and circular drumhead graphene resonators. We examined the temperature (T) dependence of the inverse of a quality factor ( Q - 1 ) to reveal what the dominant dissipation mechanism is. Our doubly-clamped trilayer resonators show a characteristic Q - 1 -T curve similar to that observed in monolayer resonators: Q - 1 ∝ T 2 above ∼100 K and ∝ T 0.3 below ∼100 K. By comparing our results with previous experimental and theoretical results, we determine that the T 2 and T 0.3 dependences can be attributed to tensile strain induced by clamping metals and vibrations at the free edges in doubly-clamped resonators, respectively. The Q - 1 -T curve in our circular drumhead resonators indicates that removing free edges and clamping metal suppresses energy dissipation in the resonators, resulting in a linear T dependence of Q - 1 in a wide temperature range.

Direct growth of graphene on SiC(0001) by KrF-excimer-laser irradiation.

In this report, we propose a direct patterning method of graphene on the SiC(0001) surface by KrF-excimer-laser irradiation. In this method, Si atoms are locally sublimated from the SiC surface in the laser-irradiated area, and direct graphene growth is induced by the rearrangement of surplus carbon on the SiC surface. Using Raman microscopy, we demonstrated the formation of graphene by laser irradiation and observed the growth process by transmission electron microscopy and conductive atomic force microscopy. When SiC was irradiated by 5000 shots of the laser beam with a fluence of 1.2 J/cm2, two layers of graphene were synthesized on the SiC(0001) surface. The number of graphene layers increased from 2 to 5-7 with an increase in the number of laser shots. Based on the results of conductive-atomic force microscopy measurements, we conclude that graphene formation was initiated from the step area, after which the graphene grew towards the terrace area by further Si evaporation and C recombination with increasing laser irradiation.

On-chip FRET Graphene Oxide Aptasensor: Quantitative Evaluation of Enhanced Sensitivity by Aptamer with a Double-stranded DNA Spacer.

We propose a molecular design for a biomolecular probe to realize an on-chip graphene oxide (GO) aptasensor with enhanced sensitivity. Here, GO works as an excellent acceptor for fluorescence resonance energy transfer. We inserted a rigid double-stranded DNA as a spacer between the GO surface and the aptamer sequence to extend the distance between a fluorescence dye and the GO surface during molecular recognition. We examined the dependence of the sensitivity on the length of the spacer quantitatively by using a 2×2 linear-array aptasensor. We used the modified aptamer with 10 and 30 base pair (bp) double-stranded DNA spacers. The signal with a 30bp-spacer was about twice as strong that with a 10bp-spacer as regards both thrombin and prostate specific antigen detections. The improvement in the sensitivity was supported by a model calculation that estimated the effect of spacer length on fluorescence recovery efficiency.

On-chip graphene oxide aptasensor for multiple protein detection.

The versatility of an on-chip graphene oxide (GO) aptasensor was successfully confirmed by the detection of three different proteins, namely, thrombin (TB), prostate specific antigen (PSA), and hemagglutinin (HA), simply by changing the aptamers but with the sensor composition remaining the same. The results indicate that both DNA and RNA aptamers immobilized on the GO surface are sufficiently active to realize an on-chip aptasensor. Molecular selectivity and concentration dependence were investigated in relation to TB and PSA detection by using a dual, triple, and quintuple microchannel configuration. The multiple target detection of TB and PSA on a single chip was also demonstrated by using a 2×3 linear-array GO aptasensor. This work enables us to apply this sensor to the development of a multicomponent analysis system for a wide variety of targets by choosing appropriate aptamers.

Synthesis and electrolytic polymerization of the ethylenedioxy-substituted terthiophene-fullerene dyad.

[reaction: see text] Two derivatives of ethylenedioxy-substituted terthiophene-fullerene dyads were newly synthesized as the precursors for polythiophene having fullerene side chains. By electrolytic oxidation of dyad 1, the charm-bracelet type polythiophene, poly-1, was obtained as a purple film, which showed electrochemical activity, electrochromism, and photoelectronic response.

Protein recognition on a single graphene oxide surface fixed on a solid support.

We study protein recognition on a graphene oxide (GO) surface using a single GO piece fixed on a solid support. The GO surface is modified by newly designed processes using pyrene as a linker to an sp2 domain in the GO, an aptamer for thrombin recognition, and a probe dye for fluorescence detection. In this system, the dye probe fluorescence, which was initially quenched by GO, is recovered when the aptamer recognizes the corresponding protein. We demonstrate the label-free and selective protein recognition for thrombin. The elementary processes of protein recognition are observed directly with a confocal laser scanning microscope and an atomic force microscope using an identical piece of GO. They indicate that proteins are recognized homogeneously on the modified GO surface. We also show that the recognition system can be installed and operated in microchannel devices.

Graphene-modified interdigitated array electrode: fabrication, characterization, and electrochemical immunoassay application.

We have developed a new procedure for fabricating interdigitated array gold electrodes (Au-IDA) modified with reduced graphene oxide (rGO). In this procedure, we coated the gold surface of the micrometer order electrodes with graphene oxide (GO) prior to the reduction and the lift-off processes to avoid short-circuiting the pair of electrodes by conductive rGO flakes after the reduction. We then studied the basic electrochemical activity of the prepared electrodes, rGO/Au-IDA, mainly on p-aminophenol (pAP), because pAP is a good probe for an electrochemical immunoassay. The voltammograms showed that denser rGO provides better electrode reactivity for pAP. We confirmed that redox cycling between the anode and cathode at the rGO/Au-IDA was established, which yields more sensitive detection than with a single electrode. As one application of the electrochemical immunoassay using the rGO/Au-IDA, we demonstrated the quantitative detection of cortisol, a stress marker, at levels found in human saliva.

Molecular design for enhanced sensitivity of a FRET aptasensor built on the graphene oxide surface.

We designed a biomolecular probe for highly sensitive protein detection by modifying an aptamer with a DNA spacer. The spacer controls the distance between a fluorescence dye and a quencher, which is crucial for FRET-based sensors. We successfully demonstrated an improvement in the sensitivity of an on-chip graphene oxide aptasensor.

Novel "lipid-flow chip" configuration to determine donor-to-acceptor ratio-dependent fluorescence resonance energy transfer efficiency.

We report on the determination of fluorescence resonance energy transfer (FRET) efficiency, which is dependent on the donor-to-acceptor (D-A) ratio, by using a new type of microchannel device called a "lipid-flow chip". The chip comprises two supported lipid bilayers (SLBs) that self-spread from either side of 10 microm wide straight lines and carry molecules embedded in them. We first show that the diffusion process that occurs when the two SLBs collide with each other in the channel and form a unified SLB can be expressed by a one-dimensional diffusion equation. Next we describe a method for determining the FRET efficiency between NBD (donor) and Texas Red (acceptor) from observations using the lipid-flow chip by employing a one-dimensional diffusion model. The advantages of our method are that all the D-A ratios are achieved in one chip, and a large number of data are recorded in one chip. The FRET efficiency varies depending on the D-A ratio under conditions whereby the concentration of the sum of the donors and acceptors is constant. The Förster radius is also estimated from our results using a known model describing two-dimensional FRET systems, which yields a radius consistent with the previously reported value for NBD and Texas Red.

Self-assembly of gold nanorods induced by intermolecular interactions of surface-anchored lipids.

Surface-modified gold nanorods (Au NRs) with 1,2-dipalmitoyl- sn-glycero-3-phosphothioethanol (DPPTE) were synthesized, and their self-assembled structures on a silicon substrate were observed using a scanning electron microscope (SEM). The Au NR-DPPTE complex formed characteristic one- and two-dimensional self-assemblies induced by intermolecular interactions of surface-anchored lipids via simple drying process. The interparticle distance between neighboring NRs was uniform at around 5.0 nm, which was consistent with the thickness of the lipid bilayer. Furthermore, we observed the anisotropic configurations of the NR complex, preferentially oriented in a lateral or perpendicular fashion, in a two-dimensional assembled structure dependent on the interfacial hydrophilicity or hydrophobicity of the silicon surface.

Supported lipid bilayer self-spreading on a nanostructured silicon surface.

We report on the self-spreading behavior of a supported lipid bilayer (SLB) on a silicon surface with various 100 nm nanostructures. SLBs have been successfully grown from a small spot of a lipid molecule source both on a flat surface and uneven surfaces with 100 nm up-and-down nanostructures. After an hour, the self-spreading SLB forms a large circle or an ellipse depending on the nanostructure pattern. The results are explained by a model that shows that a single-layer SLB grows along the nanostructured surfaces. The model is further supported by a quantitative analyses of our data. We also discuss the stability of the SLB on nanostructured surfaces in terms of the balance between its bending and adhesion energies.

Electron transport in self-assembled polymer molecular junctions.

A molecular junction of a poly(p-phenyleneethynylene)s derivative with thioacetate end groups (TA-PPE) was fabricated by self-assembling. Nanogap electrodes made by electroplating technique was used to couple thiol end groups of TA-PPE molecules. Room temperature current-voltage characteristics of the molecular junction exhibited highly periodic, repeatable, and identical stepwise features. First-principles calculations suggest that one possibility for the equidistant step is due to the opening of different conducting channels that corresponds to the unoccupied molecular orbitals of the polymer in the junction. It is interesting to see that an 18 nm long polymer is of quantized electronic structures and behaves like a quantum transport device.

Selective chemisorption of end-functionalized conjugated polymer on macro- and nanoscale surfaces.

Linear and conjugated poly(p-phenylene ethynylene)s (PPEs) with three different types of functionalized end groups (thiolacetate, isocyanide, and carboxylic acid groups) were synthesized, and their selective chemisorption behavior on various substrate surfaces were investigated using UV/vis transmission absorption spectroscopy. The UV/vis spectra of the PPEs were clearly dependent on the chemical affinity between the PPE end group and the solid surfaces. Furthermore, regarding the chemisorption of thiolacetate modified polymer on a nanoscopic gold particle surface, we visualized novel polymer-colloid nanoarchitectures such as a barbell-type nanohybrid and interconnected polymer nanowire structures that are successively linked through gold nanoparticles.