Graphene Oxide Membrane Reactor for Electrochemical Deuteration Reactions.

The deuteration of organic molecules is considerably important in organic and medicinal chemistry. An electrochemical membrane reactor using proton-conducting graphene oxide (GO) nanosheets was developed to synthesize valuable deuterium-labeled products via an efficient hydrogen-to-deuterium (H/D) exchange under mild conditions at ambient temperature and atmospheric pressure. Deuterons (D+) formed by the anodic oxidation of heavy water (D2O) at the Pt/C anode permeate through the GO membrane to the Pt/C cathode, where organic molecules with functional groups (C≡C and C═O) are deuterated with adsorbed atomic D species. Deuteration occurs in outstanding yields with high levels of D incorporation. We also achieved the electrodeuteration of a drug molecule, ibuprofen, demonstrating the promising feasibility of the GO membrane reactor in the pharmaceutical industry.

Selective Detection of CO Using Proton-Conducting Graphene Oxide Membranes with Pt-Doped SnO2 Electrocatalysts: Mechanistic Study by Operando DRIFTS.

To reduce the risk of carbon monoxide (CO) poisoning, there is a strong need for small, compact gas sensors to detect and monitor CO at ppm concentrations. In this study, we focused on detecting CO with electrochemical sensors based on proton-conducting graphene oxide (GO) nanosheets at room temperature. We found that a Ce-doped GO nanosheet membrane fitted with the sensing electrode composed of Pt (10 wt %)-doped SnO2 nanocrystals exhibits an excellent sensor response to CO at 25 °C. Pt doping of SnO2 nanocrystals has made it possible to detect CO more selectively than H2 and ethanol. The CO detection mechanism is analyzed by operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Fourier transform infrared gas cell measurements, and comprehensive density functional theory-based calculations. The results revealed that adsorption of CO occurs predominantly on Pt sites, and the adsorbed CO is anodically oxidized at the interface between the sensing electrode and proton-conducting membrane, generating the selective sensor response. The strong adsorption of CO was realized with Pt (10 wt %)-doped SnO2 nanocrystals, as revealed by the DRIFTS analysis and temperature-programed desorption technique.

Electrochemical Detection of Ethanol in Air Using Graphene Oxide Nanosheets Combined with Au-WO3.

Detection, monitoring, and analysis of ethanol are important in various fields such as health care, food industries, and safety control. In this study, we report that a solid electrolyte gas sensor based on a proton-conducting membrane is promising for detecting ethanol in air. We focused on graphene oxide (GO) as a new solid electrolyte because it shows a high proton conductivity at room temperature. GO nanosheets are synthesized by oxidation and exfoliation of expanded graphite via the Tour's method. GO membranes are fabricated by stacking GO nanosheets by vacuum filtration. To detect ethanol, Au-loaded WO3 is used as the sensing electrode due to the excellent activity of gold nanoparticles for the catalysis of organic molecules. Au-WO3 is coupled with rGO (reduced graphene oxide) to facilitate the electron transport in the electrode. Ce ions are intercalated into the GO membrane to facilitate proton transport. The sensor based on the Ce doped-GO membrane combined with Au-WO3/rGO as a sensing electrode shows good electric potential difference (ΔV) responses to ethanol in the air at room temperature. The sensor signal reaches more than 600 mV in response to ethanol at 40 ppm in air, making it possible to detect ethanol at a few ppb (parts per billion) level. The ethanol sensing mechanism was discussed in terms of the mixed-potential theory and catalysis of ethanol on Au-WO3.

A portable lipid bilayer system for environmental sensing with a transmembrane protein.

This paper describes a portable measurement system for current signals of an ion channel that is composed of a planar lipid bilayer. A stable and reproducible lipid bilayer is formed in outdoor environments by using a droplet contact method with a micropipette. Using this system, we demonstrated that the single-channel recording of a transmembrane protein (alpha-hemolysin) was achieved in the field at a high-altitude (∼3623 m). This system would be broadly applicable for obtaining environmental measurements using membrane proteins as a highly sensitive sensor.

Round-tip dielectrophoresis-based tweezers for single micro-object manipulation.

In this paper, we present an efficient methodology to manipulate a single micro-object using round-tip positive dielectrophoresis-based tweezers. The tweezers consist of a glass needle with a round-tip and a pair of thin gold-film electrodes. The round-tip, which has a radius of 3µm, is formed by melting a finely pulled glass needle and concentrates the electric field at the tip of the tweezers, which allows the individual manipulation of single micro-objects. The tweezers successfully captured, conveyed, and positioned single cell-sized liposomes with diameters of 5-23µm, which are difficult to manipulate with conventional manipulation methodologies, such as optical tweezers or glass micropipettes, due to the similarities between their optical properties and those of the media, as well as the ease with which they are deformed or broken. We used Stokes' drag theory to experimentally evaluate the positive dielectrophoresis (pDEP) force generated by the tweezers as a function of the liposome size, the content of the surrounding media, and the applied AC voltage and frequency. The results agreed with the theoretically deduced pDEP force. Finally, we demonstrated the separation of labeled single cells from non-labeled cells with the tweezers. This device can be used as an efficient tool for precisely and individually manipulating biological micro-objects that are typically transparent and flexible.

Rapid formation of size-controlled three dimensional hetero-cell aggregates using micro-rotation flow for spheroid study.

Spheroids that are formed from aggregated cells have enhanced biological function compared to individual cells. In particular, hetero-spheroids composed of different types of cells, such as hepatocytes and endothelial cells, express tissue specific functions at a high level, which is advantageous for more precise drug screening and biological research. In this study, we propose rapid formation of size-controlled three-dimensional hetero-cell aggregates consisting of hepatocytes and endothelial cells using micro-rotation flow. Based on previous data, these aggregates are expected to ultimately become hetero-spheroids. The hepatocytes are coated with collagen gel films less than 200 nm thick, which were experimentally verified to increase adhesion strength between hepatocytes and endothelial cells. Gel-coated hepatocytes and endothelial cells are collected in an array by micro-rotational flow, thereby forming hetero-cell aggregates within 2 min. This array allowed the size of the three-dimensional cell aggregates to be hydrodynamically controlled, with standard deviations of less than 19%, by varying the cell density of the medium without altering the device geometry. Endothelial cells were successfully and uniformly dispersed in the aggregates. The proposed microfluidic device, with its capability of rapidly forming size-controlled hetero-cell aggregates, will offer an efficient experimental platform for future hetero-spheroid study that will contribute to drug screening and regenerative medicine.