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This study introduces a novel microfluidic polymer chip system that employs an embedded anionic surfactant (AS) ion-selective fluorescence optode (AS fluorescence optode) as a detector for measuring AS. The AS fluorescent optode comprises a lactone form of rhodamine B (L-RB) embedded in 2-nitrophenyl octyl ether plasticized poly (vinyl chloride) membrane. The AS fluorescence optode demonstrated a linear correlation between fluorescence intensity peak heights and AS concentrations within the range of less than 20 µM under optimal flow conditions. The limit of detection for AS was approximately 0.06 µM. The microfluidic system was utilized to measure AS levels in environmental samples, such as river water and tap water., (© 2024. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

The Eu(III) distribution mechanism in single extractant-impregnated polymer-layered silica particle in a complex solution containing multiple lanthanide ions was investigated using fluorescence microspectroscopy, which was compared with the single-ion distribution system. The rate-determining step of the Eu(III) distribution was the reaction of Eu(III) with the two extractant molecules in the particle. The distribution mechanism and rate constants obtained in the multiple lanthanide ions-distribution system agreed with those of the single-ion distribution system., (© 2023. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

A microcapillary manipulation system combined with fluorescence microspectroscopy enabled us to analyze mass transfer in a single particle. In this study, we revealed the Eu(III) distribution in a single diglycolamide-derivative extractant (TODGA)-impregnated polymer-coated silica particle. The reaction of Eu(III) with two TODGA molecules in the polymer layer was the rate-limiting process, which was revealed by the relationship between the rate constants (k 1 and k -1 ) and concentrations of Eu(III) and HNO 3 . The decrease in the crosslinking degree of the polymer layer caused an increase in only k -1 . This indicates that hydrophilic environments at lower crosslinking degrees enhance the stability of the charged Eu(III) species such as Eu 3+ , Eu(NO 3 ) 2+ , and Eu(NO 3 ) 2 + ., (© 2023. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

This study reports on the electrochemical analysis of coffee extractions at different roasting levels by using a carbon nanotube (CNT) electrode. The roasting levels, ranging from 1 (low) to 6 (high), were determined according to the roasting time after fixing the roasting temperature. Level 1 roasting resulted in light roasted beans and level 6 in dark roasted ones. Based on the roasting level, the concentration of chlorogenic acids, including 3-caffeoylquinic (3CQ), 4-caffeoylquinic (4CQ), and 5-caffeoylquinic (5CQ) acid, can be determined. Cyclic voltammetry (CV) experiments revealed that the reduction current at +0.27 V was proportional to the concentration of chlorogenic acids. High-performance liquid chromatography (HPLC) revealed an inverse correlation between the roasting level and chlorogenic acid amount. The total amounts of chlorogenic acids in coffee extractions determined by HPLC were in agreement with those obtained by CV using the CNT electrode at roasting levels 1 - 5. At level 6, the amount of chlorogenic acids determined by the current peak was larger than that detected by HPLC. As a result, the chlorogenic acid amount was overestimated in the CV experiment at +0.27 V, indicating that electrochemically active materials were generated at level 6. The CV profile showed that the reduction peak at +0.10 V increased with an increase in roasting level. Thus, the peak intensity at +0.10 V can be used to evaluate the roasting level even if the concentration or dilution conditions are provided.

Herein, an electrochemical method is presented for the detection of curcumin in food using a carbon nanotube (CNT)-carboxymethylcellulose (CMC) electrode. The CNT-CMC electrode exhibited ideal characteristics for curcumin detection, namely, a high response current and adequate peak separation toward curcumin oxidation. Cyclic voltammetry revealed two oxidation peaks. In the first scan, only the irreversible peak (Peak I) was observed at a higher potential. In the second scan, the reversible redox peak pairs (Peaks II and II') appeared at lower potentials, and the potential of Peak I was decreased. Peak I corresponded to oxidation of the hydroxyl groups of the benzene ring to the catechol group via a phenoxy radical, while Peaks II and II' indicated the redox loop system of the generated catechol group. The current at Peak II was used to quantify the concentration of curcumin in the linear range of 1 - 48 μM and detection limit of 0.084 μM. The concentrations of curcumin determined by the CNT-CMC electrode in real food samples were consistent with those determined by high-performance liquid chromatography.

A flow-injection analysis (FIA) method for assaying an anionic surfactant (AS) using AS optode detector was demonstrated. The optode membrane consists of 2-nitrophenyl octyl ether as a plasticizer, lactone form rhodamine B (L-RB) and poly(vinyl chloride). The linear response concentration range of the AS optode to AS was 20 - 100 μmol dm -3 in the FIA system. The sampling rate for an AS ion (40 μmol dm -3 sodium dodecylbenzenesulfonate) in the proposed FIA system was ca. 5 samples h -1 . The AS level in commercially available laundry detergents by the proposed FIA system was determined.

Single porous silica microparticles coated with a styrene-divinylbenzene polymer (SDB) impregnated with octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) were injected into an aqueous 3 mol/L nitric acid solution containing trivalent lanthanide (Ln(III)), as a high-level liquid waste model. We used the microcapillary manipulation-injection technique; and the extraction rate of Ln(III), as an Ln(III)-CMPO complex, into the single microparticles was measured by luminescence microspectroscopy. The extraction rate significantly depended on the Ln(III), CMPO, or NO 3 concentration, and was analyzed in terms of diffusion in the pores of the microparticles and the complex formation of Ln(III). The results indicated that the rate-determining step in Ln(III) extraction was diffusion in the pore solution of the microparticles.- concentration, and was analyzed in terms of diffusion in the pores of the microparticles and the complex formation of Ln(III). The results indicated that the rate-determining step in Ln(III) extraction was diffusion in the pore solution of the microparticles.

An electrochemical analysis of polyphenols (theaflavin (TF1), theaflavin-3-gallate (TF2A), theaflavin-3'-gallate (TF2B), theaflavin-3,3'-digallate (TF3), and epigallocatechingallate (EGCG)) in a black tea infusion is demonstrated. The characterization of each polyphenol in a solution containing only a single type of polyphenol for a redox reaction at the CNT electrode with cyclic voltammetry (CV) was conducted. The oxidation peak at around +0.30 V for TF1 is assigned to catechol group in a benzotropolone ring. The oxidation peak at around +0.35 V for TF2A, TF2B, and TF3 is assigned to both of the catechol groups in the benzotropolone ring and the pyrogallol group in the gallate ring. The oxidation peak at around +0.35 V for EGCG is assigned to a pyrogallol group in the gallate ring. Current changes of those individual polyphenols at the peak potential are proportional to their concentrations (linear range 0.28 - 94 μM; detection limit 0.11 μM). The CV curve for real black tea, which is mainly composed of a mixture of the mentioned five compounds, is produced by the sum of those. The current change of the mixture solution of polyphenols is also proportional to the mass concentration of the total polyphenols and the sensitivity defined as the slope of current vs. concentration plot is independent of the ratio of the individual polyphenols. This indicates that the peak current at around +0.35 V can quantify the total amount of polyphenols in a black tea. Additionally, the shape of the CV curve can roughly estimate the ratio of [catechins]/[theaflavins]. The values for real samples determined from CVs show good agreement with that obtained by high-performance liquid chromatography.

An optode method for the determination of sulfate ion was developed. The optode membrane is 2-nitrophenyl octyl ether-plasticized poly(vinyl chloride) membrane containing tetrabromophenolphthalein ethyl ester. The method is based on formation of an ion associate between the excess of 2-aminoperimidine hydrobromide (Ap) and sulfate ion in the sample solution, and detection of the concentration of the remaining Ap ion by the optode. Under the optimal conditions, a good linear relationship was found to exist between the absorbance of the optode membrane, and concentrations of sulfate ion in a concentration range from 20 to 400 μM. The developed optode method was applied to the determination of sulfate ion in environmental water samples.

A new microfluidic polymer chip with an embedded cationic surfactant (CS) ion-selective optode (CS-optode) as a detector of flow-injection analysis (FIA) for the determination of CSs was developed. The optode sensing membrane is based on a poly(vinyl chloride) membrane plasticized with 2-nitrophenyl octyl ether containing tetrabromophenolphthalein ethyl ester. Under the optimal flow conditions of the FIA system, the CS-optode showed a good linear relationship between the peak heights in the absorbance, and the concentrations of CS in a concentration range from 50 to 400 μmol dm -3 . The sample throughput of the present system for the determination of a CS ion (300 μmol dm -3 zephiramine) was ca. 11 samples h -1 . The proposed FIA system was applied to determine the level of CS in dental rinses.

Direct and mediated electron transfer (DET and MET) in enzyme electrodes with a novel flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from fungi are compared for the first time. DET is achieved by placing a single-walled carbon nanotube (CNT) between GDH and a flat gold electrode where the CNT is close to FAD within the distance for DET. MET is induced by using a free electron transfer mediator, potassium hexacyanoferrate, and shuttles electrons from FAD to the gold electrode. Cyclic voltammetry shows that the onset potential for glucose response current in DET is smaller than in MET, and that the distinct redox current peak pairs in MET are observed whereas no peaks are found in DET. The chronoamperometry with respect to a glucose biosensor shows that (i) the response in DET is more rapid than in MET; (ii) the current at more than +0.45V in DET is larger than the current at the current-peak potential in MET; (iii) a DET electrode covers the glucose concentration range for clinical requirements and is not susceptible to interfering agents at +0.45 V; and (iv) a DET electrode with the novel fungal FAD-GDH does not affect sensing accuracy in the presence of up to 5 mM xylose, while it often shows a similar response level to glucose with other conventionally used fungus-derived FAD-GDHs. It is concluded that our DET system overcomes the disadvantage of MET.

This study aimed to develop a menadione (MD) determination method employing liquid chromatography-tandem mass spectrometry (LC-MS/MS) using a pseudo multiple reaction monitoring (MRM) technique, wherein two quadrupoles are used to monitor the same ion. Detection limits of 40 and 2 pg were obtained for MD and its deuterium-labeled form, respectively, whereas MD intra- and inter-assay coefficient of variation values were determined as 5.4 - 8.2%, with the corresponding recoveries equaling 90.5 - 109.6%. The developed method enables determination of MD in urine, plasma, cell extract, and culture media, demonstrating that pseudo multiple reaction monitoring can achieve quantification of compounds forming no suitable product ions, such as MD.

Simultaneous electrochemical determination of nicotinamide adenine dinucleotide (NADH) and ascorbic acid (AA) at a carbon nanotube electrode is presented. The discrimination of NADH and AA is conducted with the difference of peak potential by differential pulse voltammetry. Two well-distinguished anodic peaks, +0.56 and +0.26 V, due to NADH and AA are observed. The characteristics of those peaks were independent from each other. The attained characteristics for simultaneous determination of NADH and AA are (i) NADH measurement at the concentration range of 0.030 - 2.0 mM in the presence of 1.2 mM AA, and (ii) AA measurement at the concentration range of 0.030 - 2.0 mM in the presence of 2.0 mM NADH.

A sequential injection analysis (SIA) system for the determination of SCN(-) ion using a microfluidic polymer chip with an embedded SCN(-) ion-selective electrode (SCN(-)-ISE) as a detector was developed. Under the optimal flow conditions of the SIA system, the SCN(-)-ISE showed a good linear relationship between peak heights and logarithmic concentrations of SCN(-) ion with a Nernstian slope of 59.4 ± 3.8 mV decade(-1) in a concentration range from 1.0 × 10(-5) to 1.0 × 10(-1) mol dm(-3). Sample throughput of the present system for the determination of SCN(-) ion was approximately 12 samples h(-1). The proposed SIA system was applied to the determination of the level of SCN(-) ion in human saliva samples.

A solution of polyhexamethylene biguanide hydrochloride (PHMB-HCl) was titrated with a standard solution of potassium poly(vinyl sulfate) (PVSK) using crystal violet (CV) as an photometric indicator cation. The end point was detected by a sharp absorbance change due to an abrupt decrease in the concentration of CV. A linear relationship between the concentration of PHMB-HCl and the end-point volume of the titrant existed in the concentration range from 2 to 10 × 10(-6) eq mol L(-1). Back-titration was based on adding an excess amount of PVSK to a sample solution containing CV, which was titrated with a standard solution of poly(diallyldimethylammonium chloride) (PDADMAC). The calibration curve of the PHMB-HCl concentration to the end point volume of the titrant was also linear in the concentration range from 2 to 8 × 10(-6) eq mol L(-1). Both photometric titrations were applied to the determination of PHMB-HCl in a few contact-lens detergents. Back-titration showed a clear end point, but direct titration showed an unclear end point. The results of the back-titration of PHMB-HCl were compared with the content registered in its labels., (2011 © The Japan Society for Analytical Chemistry)

A nitrate ion-selective electrode (NO(3)(-)-ISE) has been developed based on tetradodecylammonium bromide as an anion exchanger and 2-nitrophenyl octyl ether as a plasticizer. The NO(3)(-)-ISE shows an almost Nernstian response to nitrate ion over a concentration range between 1.0 x 10(-6) and 1.0 x 10(-1) M, with an anionic slope of -57.7 +/- 0.7 mV/decade. The selectivity coefficients of the NO(3)(-)-ISE for nitrate ion against chloride and sulfate (log k(NO(3)(-)Cl(-))(pot) = -2.42 and log k(NO(3)(-)SO(4)(2-))(pot) = -4.33) were obtained. A microfluidic polymer chip was fabricated using polystyrene plates and stainless-steel wires as a template for the channel. The microfluidic polymer chip is composed of a mixing chip and a NO(3)(-)-ISE detector chip. The microfluidic polymer chip, integrated with a NO(3)(-)-ISE detector consisting of the NO(3)(-)-ISE and a Na(+)-ISE as a reference electrode, showed an almost Nernstian response to nitrate ion over a concentration range between 1.0 x 10(-5) and 1.0 x 10(-1) M, with an anionic slope of -54.3 +/- 1.3 mV/decade. The microfluidic polymer chip was then applied to the determination of nitrate ion in environmental water samples, such as a tap water, a well-water sample and water for agricultural use.

An optical sensor for the detection of anionic surfactants was developed. The optical sensing membrane is a 2-nitrophenyloctyl ether-plasticized poly(vinyl chloride) membrane incorporating a lactone-form Rhodamine B (L-RB). The response of the optical membrane to anionic surfactants was a result of the ion-pair coextraction of an anionic surfactant and a proton into the PVC membrane. The L-RB forms an ion associate with the extracted anionic surfactant; simultaneously, the formed L-RB ion associate is accompanied by a spectral change. Namely, the extracted anionic surfactant changes the color of the membrane from light pink to dark pink (absorption maximum; 558 nm). The optical membrane responds to anionic surfactants, such as dodecylbenzenesulfonate, dodecylsulfate and di-2-ethylhexyl sulfosuccinate in the concentration range from 1 to 50 microM.

A potentiometric titration method using a cationic surfactant as an indicator cation and a plasticized poly(vinyl chloride) membrane electrode sensitive to the cationic surfactant is proposed for the determination of polyhexamethylene biguanide hydrochloride (PHMB-HCl), which is a cationic polyelectrolyte. A sample solution of PHMB-HCl containing an indicator cation (hexadecyltrimethylammonium ion, HTA) was titrated with a standard solution of an anionic polyelectrolyte, potassium poly(vinyl sulfate) (PVSK). The end-point was detected as a sharp potential change due to an abrupt decrease in the concentration of the indicator cation, HTA, which is caused by its association with PVSK. The effects of the concentrations of HTA ion and coexisting electrolytes in the sample solution on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of PHMB-HCl and the end-point volume of the titrant exists in the concentration range from 2.0 x 10(-5) to 4.0 x 10(-4) M in the case that the concentration of HTA is 1.0 x 10(-5) M, and that from 1.0 x 10(-6) to 1.2 x 10(-5) M in the case that the concentration of HTA is 5.0 x 10(-6) M, respectively. The proposed method was applied to the determination of PHMB-HCl in some contact-lens detergents.

A cationic surfactant ion-selective field-effect transistor (cationic surfactant-ISFET) has been developed based on the tetraphenylborate derivative known as sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The cationic surfactant-ISFET shows an almost Nernstian response to tetradecyldimethylbenzylammonium chloride (Zephiramine) over a concentration range between 1.0 x 10(-6) M and 1.0 x 10(-3) M, with a slope of 58.5 +/- 1.7 mV/decade. The cationic surfactant-ISFET can be used over a range of pH values, between pH 3 and 9. The cationic surfactant-ISFET shows excellent selectivity for Zephiramine over small inorganic cations, but shows similar selectivity for other cationic surfactants, such as hexadecyltrimethylammonium and stearyltrimethylammonium ions. A microfluidic polymer chip was integrated with the cationic surfactant-ISFET, and this was fabricated using polystyrene plates and stainless wires as a template for the channel. Cationic surfactant-ISFETs used in a batch system and microchips integrated with cationic surfactant-ISFETs showed very similar performance in terms of low detection limits, slope sensitivity and the stability of the potential response. The microfluidic polymer chip was then applied to the determination of cationic surfactants in dental rinses.

We characterized three Japanese firefly species (Luciola lateralis, Luciola cruciata, and Lucidina biplagiata) and three North American firefly species (Lucidota atra, Photuris lucicrescens, and Photuris cinctipennis) based on their surface hydrocarbons. The analysis of firefly extracts by gas chromatography-mass spectrometry (GC-MS) revealed clear differences in the chromatographic profiles and mass spectra. Each firefly could be distinguished by its GC-MS profile. A major difference was observed between Japanese fireflies and North American fireflies. Among the North American fireflies, non-luminous fireflies, Lucidota atra, showed much more complicated GC-MS profile than those of luminous fireflies, Photuris lucicrescens and Photuris cinctipennis.

We propose an electron transfer-mediated amperometric enzyme biosensor based on plasma-polymerized thin film of dimethylaminomethylferrocene (DMAMF) on a sputtered gold electrode. The DMAMF plasma-polymerized film is deposited directly onto the surface of the electrode under dry conditions. The resulting thin film not only has redox sites but also is extremely thin (approximately 20 nm), adheres well onto the substrate (electrode), has a flat surface and a highly-crosslinked network structure, and is hydrophilic in nature. Glucose oxidase is densely immobilized onto the surface of DMAMF plasma-polymerized film on the gold electrode. From the electrochemical measurement, the biosensor can cover the wide range of glucose concentration (1.3 - 81 mM) at +350 mV of applied potential. The current response of the glucose biosensor was decreased by less than 5% in an aerobic solution as compared to that in an anaerobic solution. These show that the DMAMF plasma-polymerized films play a role as the electron transfer mediators between the reaction center of enzyme and the electrode.