Kazuma Mawatari

Photocatalytic generation of hydrogen by core-shell WO 3 /BiVO 4 nanorods with ultimate water splitting efficiency

Efficient photocatalytic water splitting requires effective generation, separation and transfer of photo-induced charge carriers that can hardly be achieved simultaneously in a single material. Here we show that the effectiveness of each process can be separately maximized in a nanostructured heterojunction with extremely thin absorber layer. We demonstrate this concept on WO3/BiVO4+CoPi core-shell nanostructured photoanode that achieves near theoretical water splitting efficiency. BiVO4 is characterized by a high recombination rate of photogenerated carriers that have much shorter diffusion length than the thickness required for sufficient light absorption. This issue can be resolved by the combination of BiVO4 with more conductive WO3 nanorods in a form of core-shell heterojunction, where the BiVO4 absorber layer is thinner than the carrier diffusion length while it’s optical thickness is reestablished by light trapping in high aspect ratio nanostructures. Our photoanode demonstrates ultimate water splitting photocurrent of 6.72 mA cm−2 under 1 sun illumination at 1.23 VRHE that corresponds to ~90% of the theoretically possible value for BiVO4. We also demonstrate a self-biased operation of the photoanode in tandem with a double-junction GaAs/InGaAsP photovoltaic cell with stable water splitting photocurrent of 6.56 mA cm−2 that corresponds to the solar to hydrogen generation efficiency of 8.1%.

Nanostructured WO3/BiVO4 Photoanodes for Efficient Photoelectrochemical Water Splitting

Nanostructured photoanodes based on well-separated and vertically oriented WO3 nanorods capped with extremely thin BiVO4 absorber layers are fabricated by the combination of Glancing Angle Deposition and normal physical sputtering techniques. The optimized WO3 -NRs/BiVO4 photoanode modified with Co-Pi oxygen evolution co-catalyst shows remarkably stable photocurrents of 3.2 and 5.1 mA/cm(2) at 1.23 V versus a reversible hydrogen electrode in a stable Na2 SO4 electrolyte under simulated solar light at the standard 1 Sun and concentrated 2 Suns illumination, respectively. The photocurrent enhancement is attributed to the faster charge separation in the electronically thin BiVO4 layer and significantly reduced charge recombination. The enhanced light trapping in the nanostructured WO3 -NRs/BiVO4 photoanode effectively increases the optical thickness of the BiVO4 layer and results in efficient absorption of the incident light.

Microbead-based rolling circle amplification in a microchip for sensitive DNA detection

The sensitive detection and quantification of DNA targets in the food industry and in environmental and clinical settings are issues of utmost importance in ensuring contamination-free food, monitoring the environment, and battling disease. Selective probes coupled with powerful amplification techniques are therefore of major interest. In this study, we set out to create an integrated microchemical chip that benefits from microfluidic chip technology in terms of sensitivity and a strong detection methodology provided jointly by padlock probes and rolling circle amplification (RCA). Here, we have integrated padlock probes and RCA into a microchip. The chip uses solid phase capture in a microchannel to enable washing cycles and decrease analytical area, and employs on-bead RCA for single-molecule amplification and detection. We investigated the effects of reagent concentration and amount of padlock probes, and demonstrated the feasibility of detecting Salmonella.

Surface modification by 2-methacryloyloxyethyl phosphorylcholine coupled to a photolabile linker for cell micropatterning

This report describes a new surface-treatment technique for cell micropatterning. Cell attachment was selectively controlled on the glass surface using a photochemical reaction. This strategy is based on combining 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer, which is known to reduce non-specific adsorption, and a photolabile linker (PL) for selective cell patterning. The MPC polymer was coated directly on the glass surface using a straightforward surface modification method, and was removed by ultraviolet (UV) light illumination. All the surface modification steps were evaluated using static water contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), measurements of non-specific protein adsorption, and the cell attachment test. After selective cleavage of the MPC polymer through the photomask, cells attached only to the UV-illuminated region where the MPC polymer was removed, which made the hydrophilic surface relatively hydrophobic. Furthermore, the size of the MC-3T3 E1 cell patterns could be controlled by single cell level. Stability of the cell micropatterns was demonstrated by culturing MC-3T3 E1 cell patterns for 5 weeks on glass slide. The micropatterns were stable during culturing; cell viability also was verified. This method can be a powerful tool for cell patterning research.

NMR studies of structure and dynamics of liquid molecules confined in extended nanospaces.

We fabricated an NMR cell equipped with 10-100 nm scale spaces on a glass substrate (called extended nanospaces), and investigated molecular structure and dynamics of water confined in the extended nanospaces by (1)H NMR chemical shift (delta(H)) and (1)H and (2)H NMR spin-lattice relaxation rate ((1)H- and (2)H-1/T(1)), (1)H NMR spin-spin relaxation rate ((1)H-1/T(2)), and (1)H NMR rotating-frame spin-lattice relaxation rate ((1)H-1/T(1rho)) measurements of H(2)O and (2)H(2)O. The delta(H) and (1)H- and (2)H-1/T(1) results showed that size-confinement produces slower translational motions and higher proton mobility of water, but does not affect the hydrogen-bonding structure and rotational motions. Such unique phenomena appeared in the space size of 40 to 800 nm. However, the (1)H-1/T(1) value at 40 nm was still different from that in 4 nm porous nanomaterial, because translational and rotational motions were inhibited for H(2)O molecules in the nanomaterial. By examining temperature- and deuterium-dependence of the (1)H-1/T(1) values, the molecular translational motions of the confined water were found to be controlled by protonic diffusion invoking a proton hopping pathway between adjacent water rather than hydrodynamic translational diffusion. Furthermore, we clarified that proton exchange between adjacent water molecules in extended nanospaces could be enhanced by the chemical exchange of protons between water and SiOH groups on glass surfaces, ( identical with SiO(-)...H(+)...H(2)O) + H(2)O --> triple bond SiO(-) + (H(3)O(+) + H(2)O) --> triple bond SiO(-) + (H(2)O + H(3)O(+)), based on (1)H-1/T(2) measurements. An enhancement of proton exchange rate of water due to the reduction of space sizes was verified from the results of (1)H-1/T(1rho) values, and the rate of water in the 100 nm sized spaces is larger by a factor of more than ten from that of bulk water. Such size-confinement effects were distinctly observed for hydrogen-bond solvents with strong proton-donating ability, while they did not appear for aprotic and nonpolar solvent cases. Based on these NMR results, we suggested that an intermediate phase, in which protons migrate through a hydrogen-bonding network and the water molecules are loosely coupled within 50 nm from the surface, exists mainly in extended nanospaces. This model could be supported by a three-phase theory based on the weight average of three phases invoking the bulk, adsorbed, and intermediate phases.

Femto Liquid Chromatography with Attoliter Sample Separation in the Extended Nanospace Channel

A liquid chromatography system, comprising a separation column with a width and depth of a few hundred nanometers, was fabricated on a glass microchip (femto liquid chromatography, fLC). The size of this system was approximately 10(11) times smaller than that of a conventional LC system, the flow rate was subpicoliter/minute, and the injection volume was a few hundred attoliters. The fLC system did not require packing stationary phase and was capable of separating solutes with different molecular charges (fluorescein and sulforhodamine B) that could not be separated on a conventional LC column whose surface was covered with the same functional group as that of the column of the fLC system. The fLC system represented herein overcomes limitations of conventional chromatography separation, namely, heterogeneity of the stationary phases and eddy diffusion. Scale-down of the chromatography system brought advantages not only in reduction of sample volume but also in separation efficiency. The fLC system can analyze a very small amount of sample with high efficiency and will be useful in analyzing small samples, such as single cells and synaptic clefts. fLC greatly influences and benefits various fields such as life sciences, medicine, environmental science, and manufacturing by the improvement of separation technology.

Microchip-based cell analysis and clinical diagnosis system

Cell analysis and clinical diagnosis systems are now becoming the largest field of application for microchip-based analytical systems. Technological advantages include: small volume, fast analysis time, highly integrated analytical functions, easy operation and small size. For these purposes, basic methodologies for general micro-integration and basic technologies, including fluidic control and ultrasensitive detection, are required. In this review, we introduce our approach to the general integration of various analytical functions and the application of cell analysis systems with cultured cells in microchannels, as well as practical analytical systems for clinical diagnosis utilizing human serum samples.

Viscosity and Wetting Property of Water Confined in Extended Nanospace Simultaneously Measured from Highly-Pressurized Meniscus Motion

Understanding fluid and interfacial properties in extended nanospace (10-1000 nm) is important for recent advances of nanofluidics. We studied properties of water confined in fused-silica nanochannels of 50-1500 nm sizes with two types of cross-section: (1) square channel of nanoscale width and depth, and (2) plate channel of microscale width and nanoscale depth. Viscosity and wetting property were simultaneously measured from capillary filling controlled by megapascal external pressure. The viscosity increased in extended nanospace, while the wetting property was almost constant. Especially, water in the square nanochannels had much higher viscosity than the plate channel, which can be explained considering loosely coupled water molecules by hydrogen bond on the surface within 24 nm. This study suggests specificity of fluids two-dimensionally confined in extended nanoscale, in which the liquid is highly viscous by the specific water phase, while the wetting dynamics is governed by the well-known adsorbed water layer of several-molecules thickness.

Bonding of glass nanofluidic chips at room temperature by a one-step surface activation using an O2/CF4 plasma treatment

A technical bottleneck to the broadening of applications of glass nanofluidic chips is bonding, due to the strict conditions, especially the extremely high temperatures (~1000 °C) and the high vacuum required in the current glass-to-glass fusion bonding method. Herein, we report a strong, nanostructure-friendly, and high pressure-resistant bonding method, performed at room temperature (RT, ~25 °C) for glass nanofluidic chips, using a one-step surface activation process with an O(2)/CF(4) gas mixture plasma treatment. The developed RT bonding method is believed to be able to conquer the technical bottleneck in bonding in nanofluidic fields.

Development of a Measurement Technique for Ion Distribution in an Extended Nanochannel by Super-Resolution-Laser-Induced Fluorescence

Ion behavior confined in extended nanospace (10(1)-10(3) nm) is important for nanofluidics and nanochemistry with dominant surface effects. In this paper, we developed a new measurement technique of ion distribution in the nanochannel by super-resolution-laser-induced fluorescence. Stimulated emission depletion microscopy was used to achieve a spatial resolution of 87 nm higher than the diffraction limit. Fluorescein was used for ratiometric measurement of pH with two excitation wavelengths. The pH profile in a 2D nanochannel of 410 nm width and 405 nm depth was successfully measured at an uncertainty of 0.05. The excess protons, showing lower pH than the bulk, nonuniformly distributed in the nanochannel to cancel the negative charge of glass wall, especially when the electric double layer is thick compared to the channel size. The present study first revealed the ion distribution near the surface or in the nanochannel, which is directly related to the electric double layer. In addition, the obtained proton distribution is important to understand the nanoscale water structure between single molecules and continuum phase. This technique will greatly contribute to understanding the basic science in nanoscale and interfacial dynamics, which are strongly required to develop novel miniaturized systems for biochemical analysis and further applications.