Countercurrent laminar microflow for highly efficient solvent extraction.
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Journal Article↗
Biomedical subjects
Akihide Hibara
Publications and source records attributed to Akihide Hibara.
Application of a micro multiphase laminar flow on a microchip for extraction and determination of derivatized carbamate pesticides.
Determination of carbamate pesticides such as carbaryl, carbofuran, propoxur and bendiocarb was demonstrated on a microchip with newly designed microchannels developed for efficient solvent extraction. The pesticides were hydrolyzed to corresponding naphthols, coupled with p-nitrobenzenediazonium fluoroborate reagent, and then extracted into 1-butanol as colored azo derivatives and detected with a thermal lens microscope. Optimum flow rates for the aqueous and organic phases were evaluated in the continuous-flow chemical process established in the microchip. The calibration lines showed good linearity in the range of concentrations of 0.03 - 3 ppm (10(-7) - 10(-5) M) and a mass detection limit down to a nanogram level was achieved that is at least two orders of magnitude lower than the LODs for conventional spectrophotometric methods. Azo derivatives of the pesticides were successfully separated and identified by micellar electrokinetic chromatography (MEKC) using a sample prepared on a bulk scale.
Journal Article↗
Pressure-driven flow control system for nanofluidic chemical process.
We developed a novel flow control system for a nanofluidic chemical process. Generally, flow control in nanochannels is difficult because of its high-pressure loss with very small volume flow rate. In our flow control method, liquid pressure in a microchannel connected to the nanochannels is regulated by utilizing a backpressure regulator. The flow control method was verified by using simple structured microchip, which included parallel nanochannels. We found that the observed flow rate was three times lower than the value expected from Hagen-Poiseuille's equation. That implied a size-dependent viscosity change in the nanochannels. Then, we demonstrated mixing of two different fluorescent solutions in a Y-shaped nanochannel and also a proton exchange reaction in the Y-shaped nanochannel. The flow control method will contribute to further integration of nanochemical systems.
Microfluidics↗
Microchip-based liquid-liquid extraction for gas-chromatography analysis of amphetamine-type stimulants in urine.
A microchip-based liquid-liquid extraction for the gas chromatography analysis of urine for amphetamine-type stimulants has been developed. Partially modified microchannels with the capillarity restricted modification (CARM) method were employed for stabilizing the interface consisting of 1-chlorobutane and alkalized urine. Reliability of the microchip-based extraction was evaluated with respect to linearity, trueness and precision. As a practical demonstration, methoxyphenamine hydrochloride (50 mg) was administered to three healthy volunteers, and the concentration of methoxyphenamine in their urine was determined by both methods for comparison. This study showed the potential of pressure-driven microfluidics to contribute to the rapid automation analysis in forensic toxicology.
Adult↗
Supercooled micro flows and application for asymmetric synthesis.
Supercooled micro flow in microchannels was demonstrated. In order to clarify fundamental properties of the supercooling state in microchannels, freezing temperature was measured in the microchannels having widths ranging from 70 microm to 300 microm. The freezing temperature decreased with decreasing width of the microchannel when the microchannel wall was chemically modified with octadecylsilane group. The lowest freezing temperature was observed as -28 degrees C for water in the 70 microm wide microchannel. By contrast, the freezing temperature was -15 degrees C and did not depend on width when a microchannel with a bare glass surface was used. Next, the freezing point was measured with flow rates ranging from 0.1 to 2.0 microl min(-1) and no dependence on flow rate was observed. Then, the supercooled micro flow was applied to an asymmetric reaction in micro two-phase flow of aqueous and CH2Cl2 phases. As expected from thermodynamic prediction, enantiomeric selectivity increased in the supercooled state of water.
Catalysis↗
UV excitation thermal lens microscope for sensitive and nonlabeled detection of nonfluorescent molecules.
An ultrasensitive and nonlabeled detection method of nonfluorescent molecules on a microchip was developed by realizing a thermal lens microscope (TLM) with a 266-nm UV pulsed laser as an excitation light source (UV-TLM). Pulsed laser sources have advantages over continuous-wave laser sources in more compact size and better wavelength tuning, which are important for microchip-based analytical systems. Their disadvantage is difficulty in applying a lock-in amplifier due to the high (>10(4)) duty ratio of pulse oscillation. To overcome this problem, we realized a quasi-continuous-wave excitation by modulating the pulse trains at approximately 1 kHz and detecting the synchronous signal with a lock-in amplifier. The optimum pulse repetition frequency was obtained at 80 kHz, which was reasonable considering thermal equilibrium time. Furthermore, a permissible flow velocity in the range of 6.6-19.8 mm/s was found to avoid sensitivity decrease due to photochemical reactions and thermal energy dissipation. Under these conditions, we detected adenine aqueous solutions on a fused-silica microchip without labeling and obtained a sensitivity that was 350 times higher than that in a spectrophotometric method. The sensitivity was enough for detection on a microchip with an optical path length that was 2-3 orders shorter than that in conventional cuvettes. Finally, the UV-TLM method was applied to liquid chromatography detection. Fluorene and pyrene were separated in a microcolumn and detected in a capillary (50-microm inner diameter) with 150 times higher sensitivity than a spectrophotometric method. Our method provides highly sensitive and widely applicable detections for various analytical procedures and chemical syntheses on microchips.
Adenine↗
Circular dichroism thermal lens microscope for sensitive chiral analysis on microchip.
A novel chiral detector, a circular-dichroism thermal lens microscope (CD-TLM), was developed to realize sensitive and selective detection of small volume chiral samples on a microchip. To realize chiral recognition on TLM, an excitation beam was phase-modulated at a frequency of 1.2 kHz, and left-circularly polarized light (LCPL) and right-circularly polarized light (RCPL) were generated. Then, the differential light absorption between LCPL and RCPL, which is the CD effect, was detected as thermal lens signal intensity and phase. As a standard sample, optically active tris(ethylenediamine)cobalt(III) [Co-(en)3]3+I3- aqueous solutions were used for performance evaluations. First, we verified the basic principle for selective chiral analysis by comparing the signals in intensity-modulation and phase-modulation modes of the excitation beam. Also, we found that the g-factor, which is significant for determining enantiomeric excess, agreed well with the value obtained by the CD spectrometer. The limit of detection (LOD) for enantiopure [Co-(en)3]3+I3- was 6.3 x 10(-5) M (1.9 x 10(-7) abs) for (-)-Co(en)3(3+), and the sensitivity in absorbance units was more than 250 times higher than that in a CD spectrophotometer. Finally, we demonstrated enantiomeric excess determination on a microchip. The LOD was 1.7% (8.5 x 10(-7) abs) for (-)-Co(en)3(3+) and at least one order superior to the LOD of a CD spectrometer. The applicability of CD-TLM for sensitive chiral analysis on a microchip was verified, and CD-TLM is expected to be promising for microchip-based chiral synthesis and analysis systems.
Journal Article↗
Liquid filling method for nanofluidic channels utilizing the high solubility of CO2.
We developed a fabrication method and a liquid filling method for a nano chemical reactor that used Y-shaped nanochannels specially designed for mixing and reacting. In order to reduce the pressure loss and to utilize the characteristics of the nanochannel, inlet microchannels were fabricated just beside the nanochannels. We investigated an initial liquid filling method into the nanochannels that ensured there were no air bubbles that could cause a flow stack due to the capillary pressure. In our method, the micro- and nanochannels were filled with carbon dioxide and any remaining air during the initial liquid introduction was dissolved utilizing the high solubility of carbon dioxide. We propose that chemical reactions in nanospaces can be realized by utilizing these fabrication and liquid introduction techniques.
Journal Article↗
Miniaturized thermal lens and fluorescence detection system for microchemical chips.
We have developed a miniaturized two-way detection system using thermal lens and fluorescence spectroscopies for microchip chemistry. The system was composed of laser diode (LD) modules, fiber-based optics combined with a gradient index lens, and miniaturized detection units for thermal lens and fluorescence signals. The detection limits in the thermal lens and fluorescence spectroscopies were 6.3 x 10(-9)M for Ni(II) phthalocyanine tetrasulfonic acid and 3.0 x 10(-9)M for cy5, respectively. The performance of the system with the miniaturized thermal lens was equivalent to that of a conventional thermal lens microscope. The fluorescence sensitivity was comparable to sensitivities offered by conventional miniaturized systems.
Miniaturization↗
Surface modification method of microchannels for gas-liquid two-phase flow in microchips.
A capillarity restricted modification method for microchannel surfaces was developed for gas--liquid microchemical operations in microchips. In this method, a microstructure combining shallow and deep microchannels and the principle of capillarity were utilized for chemical modification of a restricted area of a microchannel. A hydrophobic--hydrophilic patterning in microchannels was prepared as an example for guiding gas and liquid flows along the respective microchannels. Validity of the patterning was confirmed by measuring aqueous flow leak pressure from the hydrophilic microchannel to the hydrophobic one. The leak pressure of 7.7-1.1 kPa agreed well with that predicted theoretically from the Young-Laplace equation for the microchannel depth of 8.6-39 microm. In an experiment to demonstrate usefulness and effectiveness of the method, an air bubble was first introduced into the hydrophilic microchannel and purged from the hydrophobic-hydrophilic patterned microchannels. Next, the patterning structure was applied to remove dissolved oxygen by contacting the aqueous flow with a nitrogen flow. The concentration of dissolved oxygen decreased with contact time, and its time course agreed well with numerical simulation. These demonstrations showed that the proposed patterning method can be used in general microfluidic gas-liquid operations.
Biomechanical Phenomena↗
Tunable thermal lens spectrometry utilizing microchannel-assisted thermal lens spectrometry.
A tunable thermal lens spectrometry system was developed for microchip analysis. The system utilized a Xe lamp as an excitation source, instead of a laser. The system can measure the absorption spectrum of a turbid solution without disturbance of the light scattering background.
Journal Article↗
Grazing-exit and micro X-ray fluorescence analyses for chemical microchips.
Grazing-exit x-ray fluorescence (GE-XRF) and micro x-ray fluorescence (micro-XRF) methods were applied to chemical microchips as a detection method. Since an energy-dispersive x-ray detector was used, the simultaneous detection of multiple elements was possible. An analyzing region was especially designed on the microchip so that a sample solution could be dried and concentrated in a suitable area corresponding to the size of the primary x-ray beam. Finally, it was confirmed that both analytical methods could be combined well for use with a microchip. In GE-XRF, the background intensity in the XRF spectrum was reduced at grazing-exit angles. In addition, a good relationship between the x-ray fluorescence intensities and the concentrations of standard solutions that were introduced into the microchip was obtained. This indicates that the GE-XRF method is feasible for trace elemental analysis in chemical microchip systems. In micro-XRF, an attempt was made to concentrate and dry the analyte within a small analyzing region. The preliminary results indicated that the micro-XRF method could be applied for the analysis of microchips.
Journal Article↗
Spectroscopic analysis of liquid/liquid interfaces in multiphase microflows.
Microscopic quasi-elastic laser scattering (muQELS) spectroscopy has been developed for analysis of interfacial phenomena at laminar multiphase microflow in a microchannel. Transport phenomena of a metal chelate through a water/toluene interface were measured, and transient adsorption of the chelate in the initial step of the transport was measured. A water/methanol miscible interface was also measured, and the interfacial free energy of a miscible interface was determined for the first time. The muQELS is expected to be very effective not only for physicochemical investigations of transport and mixing, but also for elemental process analysis of heterogeneous reactions.
Journal Article↗
Microchip-based chemical and biochemical analysis systems.
This review focuses on chemical and biochemical analysis systems using pressure-driven microfluidic devices or microchips. Liquid microspace in a microchip has several characteristic features, for example, short diffusion distances, high specific interfacial area and small heat capacity. These characteristics are the key to controlling micro unit operations and constructing new integrated chemical systems. By combining multiphase laminar flow and the micro unit operations, such as mixing, reaction, extraction and separation, continuous flow chemical processing systems are realized in the microchip format. By applying these concepts, several different analysis systems were successfully integrated on a microchip. In this paper, we introduce the microchip-based chemical systems for wet analysis of cobalt ion, multi-ion sensors, immunoassay, and cellular analysis.
Animals↗
Microchannel-assisted thermal-lens spectrometry for microchip analysis.
Microchannel-assisted thermal lens spectrometry (MATLS) was developed for microchip analysis. This method utilized a photothermal effect in a very small space and rapid thermal conduction between a solid-liquid interface to produce a temperature gradient in the microchannel. In order to examine the mechanism experimentally, we constructed a detection system of laser defocus setup in which an excitation beam was not tightly focused, but it irradiated the microchannel homogeneously. The signal intensity dependence on modulation frequency of excitation and on solvent was investigated with the laser defocusing setup. The results of this investigation indicated that the mechanism of MATLS worked as expected. Since the mechanism of MATLS does not require directivity and coherence of the laser beam, other incoherent lightsources can be used as excitation light for sensitive detections. Finally, we considered some future applications utilizing the mechanism.
Semiconductors↗
Chemicofunctional membrane for integrated chemical processes on a microchip.
Here we report a design and synthesis of a chemically functional polymer membrane by an interfacial polycondensation reaction and multilayer flow inside a microchannel. Single and parallel dual-membrane structures are successfully prepared by using organic/aqueous two-layer flow and organic/aqueous/organic three-layer flow inside the microchannel followed by an interfacial polycondensation reaction. By using the inner-channel membrane, permeation of ammonia species through the inner-channel membrane is successfully achieved. Furthermore, horseradish peroxidase is immobilized on one side of the membrane surface to integrate the chemical transform function onto the inner-channel membrane. Here substrate permeation through the membrane and subsequent chemical transformation at the membrane surface are realized. The polymer membrane prepared inside the microchannel has an important role in ensuring stable contact of different phases such as gas/liquid or liquid/ liquid and the permeation of chemical species through the membrane. Furthermore, membrane surface modification chemistry allows chemical transformation of permeated chemical species. These methods are expected to lead to development of complicated and sophisticated chemical systems involving membrane permeation and chemical reactions.
Journal Article↗
Chemical processing on microchips for analysis, synthesis, and bioassay.
This review describes our recent research on miniaturization of chemical systems. We have developed a miniaturization methodology based on pressure-driven multiphase laminar flow and a highly sensitive detection tool, the thermal lens microscope. Some representative applications of the methodology in the fields of analysis, synthesis, and bioassay are described.
Microscopy↗
An interface chip connection between capillary electrophoresis and thermal lens microscope.
A thermal lens microscope (TLM) detection of capillary electrophoresis (CE) utilizing microchip technology was developed. Fused-silica capillaries with an inner diameter of 50 microm were directly connected to a microchannel in a microchip. The detection limit by TLM was estimated as 2.8 x 10(-7) absorbance by measuring pure water. The detection limit of derivatized amino acids determined by CE-TLM was estimated as 2.4 x 10(-8) M, which was 100 times lower than that of conventional absorbance detection.
Amino Acids↗