Analytical Sciences
Online ISSN : 1348-2246
Print ISSN : 0910-6340
ISSN-L : 0910-6340
Volume 34 , Issue 10
Showing 1-19 articles out of 19 articles from the selected issue
Highlights
Original Papers
  • Yawei LIANG, Xinna WANG, Huanle FANG, Ningjuan HAN, Cuiling WANG, Zhiq ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1111-1115
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    A new colorimetric probe, based on tryptanthrin derivative (TR-A), has been successfully synthesized. The probe shows good selectivity and sensitivity for Cu2+ over 12 competing metal ions in a 10 mM Tris–HCl buffer solution (pH 5.5). A significant peak at 623nm appears in the UV-Vis absorption of TR-A-Cu2+, and a noteworthy color change is observed with the naked eye from aquamarine blue to light orange. The interaction of TR-A and Cu2+ are proven to form a 1:1 binding stoichiometry; this identifying is expected to be completed within 1 min. The probe with a limit of detection (16 nM, R2 = 0.9934) shows excellent potential to determine Cu2+ in analysis systems.

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  • Chaoman ANG, Doudou LOU, Linling HU, Wei CHEN, Yefei ZHU, Zhirui GUO, ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1117-1123
    Published: October 10, 2018
    Released: October 10, 2018
    [Advance publication] Released: June 01, 2018
    JOURNALS FREE ACCESS

    In this research, we developed a rapid and easy-to-operate point-of-care testing (POCT) strip based on fluorescent affinity immunochromatography to quantitatively determine HbA1c concentrations in whole blood. This assay, based on a sandwich method performed on test strips, effectively utilized the principle of an affinity chromatography column, which was commonly used in the detection of HbA1c, and the technology of traditional fluorescence immunochromatographic test strips (FICTS) were combined. In our test strips, the test line of traditional FICTS was transformed into the region of affinity chromatography, while improving the linearity and reducing the interference of the precursor of HbA1c and hemoglobin variants. The test strips could quantitatively detect HbA1c over a wide range (3 – 13.8%) with excellent linearity (R2 > 0.99), and the assay accuracy was demonstrated by comparing with high-performance liquid chromatography (HPLC) (R2 > 0.95). The simple, rapid, effective and quantitative strips will provide a novel method for the detection of HbA1c in clinical diagnosis.

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  • Yuji TSUCHIDO, Aya YAMASAWA, Takeshi HASHIMOTO, Takashi HAYASHITA
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1125-1130
    Published: October 10, 2018
    Released: October 10, 2018
    [Advance publication] Released: June 01, 2018
    JOURNALS FREE ACCESS

    Dipicolylamine-modified fluorescent silica nanoparticles were prepared by introducing dipicolylamine to the surface of silica nanoparticles possessing terminal amines. We examined the selectivities of dipicolylamine-hydroxycoumarin carbonate (dpa-HCC) and dpa-HCC/fluorescent silica nanoparticles (FSiNP) for metal ions and phosphate anions. The dipicolylamine-modified silica nanoparticles responded to PPi, Tri and Pb2+, indicating novel selectivity derived from the assembly effect of dpa-HCC on the silica nanoparticle surface. Surface-modified fluorescent silica nanoparticles are expected to be used as a sensor for environmental and biological applications.

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  • Tingting GU, Hong-qi XIA, Yue HU, Yongqi JIANG
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1131-1135
    Published: October 10, 2018
    Released: October 10, 2018
    [Advance publication] Released: June 01, 2018
    JOURNALS FREE ACCESS

    A reagent-less electrochemical DNA biosensor for rapid non-electroactive polycyclic organic compounds (POCs) screening and detection was proposed. In this method, methylene blue (MB) was incorporated into DNA/chitosan polyion complex membrane and then modified onto a glassy carbon electrode (GCE). The electrochemical analysis for the prepared DNA-MB/chitosan/GCE showed that the modified electrode exhibited high electrochemical activity and stability. The addition of tetracycline hydrochloride (TC), a model analyte of non-electroactive POCs, resulted in an obvious peak current decrease in DNA-MB/chitosan/GCE, and this electrochemical response was affected by the DNA type and MB/DNA ratio in the modified electrodes. Ultraviolet-visible (UV-Vis) absorption spectroscopy was utilized to furthermore investigate the interaction between TC and DNA-MB/chitosan/GCE. As a result, a competitive interaction and displacement effect between TC and the intercalated MB was proposed. In our condition, the prepared DNA-MB/chitosan/GCE showed high sensitivity to POCs and had almost no response to common interferences. Besides, the good stability and reproducibility of the prepared electrode made it suitable for practical use.

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  • Yukina MATSUI, Yuki KITAZUMI, Osamu SHIRAI, Kenji KANO
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1137-1142
    Published: October 10, 2018
    Released: October 10, 2018
    [Advance publication] Released: June 01, 2018
    JOURNALS FREE ACCESS

    Amperometric biosensors were constructed for the simultaneous detection of lactate enantiomers. The enantioselectivity of the sensor is based on NAD-dependent l- and d-lactate dehydrogenases that, respectively, oxidize l- and d-lactates into pyruvate. The NADH formed during the enzymatic reduction was catalytically oxidized at Meldola’s blue-adsorbed mesoporous electrodes. Stable amperometric measurements were performed in a two-electrode system using Ag|AgCl|sat. KCl as a counter electrode via a salt bridge. The response of the sensor reached a pseudo-steady state within 60 s. The agreement of the sensitivities for l- and d-lactates and the pseudo-steady-state characteristics of the sensors demonstrate that the current is strongly influenced by the diffusion of lactates at the edge of the electrode, enabling reproducible measurements. The pseudo steady-state characteristics are also realized at the chip-type electrode. The sensor was successfully applied for the detection of d- and l-lactates in horse serum.

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  • Yasin ARSLAN, Burcu KABAK, Digdem TRAK, Erdal KENDÜZLER
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1143-1147
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    In this study, Amberlite CG-120 adsorbent was used for the separation/preconcentration of Ni(II) ions in commercial drinking, spring and lake water samples before detection by flame atomic absorption spectrometry. Various optimization parameters for Ni(II) determination, such as pH, eluent type and concentration, sample and eluent flow rates, amount of adsorbent, were investigated to obtain better sensitivity, accuracy, precision and quantitative recovery. Furthermore, the interference effects of some ions on the recovery efficiency of Ni(II) were also investigated. The optimum experimental parameters were obtained in the case of pH 1; 5 mL of 4 mol L−1 HCl for eluent and 0.3 g for the adsorbent amount. The limit of detection was found to be 0.58 μg L−1 and linearity ranged from 5 to 50 μg L−1. The accuracy of the method was tested by the certified reference material of TMDA-70.2 Ontario Lake Water at a 95% confidence level.

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  • Ikuo UETA, Risa TAKENAKA, Koji FUJIMURA, Tomotaka YOSHIMURA, Shoji NAR ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1149-1153
    Published: October 10, 2018
    Released: October 10, 2018
    [Advance publication] Released: June 08, 2018
    JOURNALS FREE ACCESS

    In this study, a solid-phase extraction-type collection device, with styrene-divinylbenzene polymer particles (Sunpak-H) as the adsorbent, was used for the quantitative determination of phthalate esters in air samples. The collection and elution recoveries of eight volatile phthalate esters, i.e., dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, dibutyl phthalate, butyl-benzyl phthalate, di(2-ethylhexyl) phthalate, and dioctyl phthalate, were quantitatively evaluated. All analytes were collected using the device up to a sampling volume of 10000 L at a sampling temperature of 35°C without breakthrough. During air collection, moisture was not trapped on the adsorbent. The collected analytes were completely eluted from the device by passing 3 mL of acetone. The eluted solvent was injected into a gas chromatography–mass spectrometry system after the eluted solvent was concentrated, if necessary. After washing the adsorbent using acetone, the device could be reused more than 50 times. The limit of quantification for the analytes was less than 1 ng L−1 in air at a sampling volume of 600 L with solvent concentration. This device was successfully applied for the quantitative determination of phthalate esters in real air samples, including indoor and in-car air.

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  • Hao ZHANG, Yanan GUAN, Xiaoshuang LI, Lili LIAN, Xiyue WANG, Wenxiu GA ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1155-1161
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    This paper describes a novel method for label-free mercury(II) ion detection based on exonuclease III-induced target signal recycling amplification using double-stranded DNA templated copper nanoclusters. The synthesized DNA-Cu nanoclusters were used with exonuclease III loop amplification technology for ultra-high sensitivity detection of mercury(II) ions, which were detected by significantly decreased fluorescence intensity. Under the optimal experimental conditions, there was a clear linear relationship between Hg2+ concentration in the range of 0.04 to 8 nM and fluorescence intensity. The detection limit for Hg2+ was 4 pM. In addition, the interference of other metal ions on the mercury(II) ion detection was also studied. To confirm the application of the fluorescent sensor, it was applied to determine the concentrations of mercury(II) ions in tap water, and the results showed that the method can be used to detect mercury(II) ions in water samples successfully.

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  • Appan ROYCHOUDHURY, Suddhasatwa BASU, Sandeep Kumar JHA
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1163-1169
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    An amperometric biosensor has been developed for highly efficient and sensitive detection of catechol using Prussian blue (PB)-coated nickel oxide (NiO) nanoparticles (NPs) as a matrix for the immobilization of tyrosinase enzyme. The NiO NPs were synthesized by sol-gel method using sodium dodecyl sulphate as anionic surfactant and the surface of the synthesized NiO NPs was modified with PB to enhance electrocatalytic activity and to prevent surface aggregation. After confirmation of successful synthesis of the PB-NiO NPs from transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopic (EDS) studies, the prepared NPs were deposited onto a working electrode of a commercially available screen printed carbon electrode (SPCE) substrate. The tyrosinase enzyme was covalently immobilized onto the PB-NiO deposited SPCE for selective detection and estimation of catechol through electrochemical methods via cyclic voltammetry (CV) and chronoamperometric techniques. The functionalization of tyrosinase on the electrode surface was verified by atomic force microscopy (AFM) and scanning electron microscopic (SEM) techniques and the electrochemical response studies of the proposed biosensor showed high sensitivity of 0.954 μA/μM for catechol in a wide linear range (1 – 50 μM) with low detection limit (LOD) of 0.087 μM. The developed sensor also exhibited a fast response time of 27 s and decent selectivity for catechol detection.

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  • Edgar NAGLES, Olimpo GARCÍA-BELTRÁN
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1171-1175
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    A simple method to determine Allura Red (AR) in cherry gelatin, chili sauce and strawberry juice by square-wave adsorptive stripping voltammetry (SWAdV) in the presence of cetylpyridinium bromide (CPB) is reported. Using a glassy carbon electrode (GCE), Amaranth (AM), Ponceau 4R (P-4R) and AR were oxidized to very close potential values in medium acid pH 3.0 with phosphate buffer solution (PBS), making selective AR detection impossible. Under these conditions AM, P-4R and AR were oxidized at 0.80, 0.77 and 0.81 V, respectively. When small amounts of CPB were added, an AR-CPB aggregate was formed. This change displaced the oxidation almost 0.14 V in the direction of the most positive potential and increased the current almost 50%, while AM and P-4R were oxidized at almost the same potential. Under these conditions, the selective determination of AR in food was possible. Detection limit was 0.032 μmol L−1. Finally, the method was successfully applied to the determination of AR in these foods.

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  • Ryosuke TAKEUCHI, Yu SUGIMOTO, Yuki KITAZUMI, Osamu SHIRAI, Jun OGAWA, ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1177-1182
    Published: October 10, 2018
    Released: October 10, 2018
    [Advance publication] Released: June 15, 2018
    JOURNALS FREE ACCESS

    Shewanella can transfer electrons to various extracellular electron acceptors. We electrochemically investigated the pathway of extracellular electron transfer from Shewanella strain Hac319 to electrodes. A resting cell suspension of Shewanella strain Hac319 containing lactate produced a steady-state sigmoidal wave in the presence of flavin mononucleotide (FMN) in cyclic voltammetry, but not in the absence of FMN. A harvested cell suspension without cell-washing also produced a similar catalytic wave without any external addition of free FMN. The midpoint potentials of the two sigmoidal waves were identical to the redox potential of free FMN. The data indicate that FMN secreted from the Shewanella strain Hac319 works as an electron-transfer mediator from the cell to electrodes. An addition of cyanide to a resting cell suspension of Shewanella strain Hac319 increased the rate of the FMN reduction in the presence of lactate, while it decreased the respiration rate. By considering the fact that cyanide is coordinated to the heme moiety of hemoproteins and shifts the redox potential to the negative potential side, the data indicate that the electron derived from lactate is predominantly transferred in a down-hill mode from an electron donor with a redox potential more negative than that of FMN without going through outer membrane cytochromes c molecules.

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  • Naoyuki YASAKA, Naoya KISHIKAWA, Takumi HIGASHIJIMA, Kaname OHYAMA, Na ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1183-1188
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    Aryl halides are a very important category of compounds that include many vital drugs and key industrial additives, such as clofibrate and bromobenzene, respectively. Due to their importance, our research group previously developed a novel fluorescence labeling approach for their analysis using a fluorescent aryl boronic acid as a reagent, based on the Suzuki coupling reaction. This coupling reaction was successfully applied for the determination of aryl halides in biological fluids; however, there was a limitation of low reactivity towards ortho-substituted aryl halides. In the present study, a novel fluorescence derivatization approach for aryl halides was developed using, 2-(4-ethynylphenyl)-4,5-diphenyl-1H-imidazole (DIB-ET) as a fluorescent alkyne reagent, based on the Sonogashira coupling reaction. DIB-ET reacted with aryl bromides in the presence of palladium and copper as catalysts, yielding fluorescent derivatives that could be subsequently determined by an HPLC system with fluorescence detection. The detection limits (S/N = 3) for aryl bromides were in the range of 14 – 23 nM, which is 3.5 – 18-times more sensitive than our previously developed approach, Suzuki coupling derivatization. Moreover, in contrast to the previous technique, the reactivity of DIB-ET to ortho-substituted aryl bromides was almost equivalent to that of the para-substituted aryl bromides. Hence, by using this newly developed approach we could label the aryl halides with more sensitivity and reactivity. Finally, the proposed method was successfully applied for the selective determination of aryl bromides in human serum with good recovery (84.6 – 107%), which proves the ability of the developed method to determine occupational exposure to aryl halides.

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  • Junko JOHZUKA, Toshihiro ONA, Masatoshi NOMURA
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1189-1194
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    In anti-cancer drug (candidate) screening, there is the need for evaluation at physiological concentrations similar to in vivo. This is often performed by three-dimensionally (3D) cultured cells; however, it requires a long culture period of 2 – 4 weeks with tedious experimental procedures. Here, we report on a high precision surface plasmon resonance (HP-SPR)-3D system. We developed the system with average fluctuation of 50 ndeg s−1 using two-dimensionally cultured cells attached onto a sensor chip by applying collagen on the top to change their activity into in vivo-like conditions without cell division. It allowed in vivo-like phenotypic screening for anti-cancer drugs within 1 h of drug addition. The data were collected as the stable linear signal change parts for at least 5 min after 25 min following drug addition. The results provided compatibility to clinically related chemosensitivity test for anti-cancer (P <0.001) using two cell lines of pancreatic cancer and three anti-cancer drugs to represent differences in individual gene expression and drug mode of action.

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  • Takahiko MITANI, Hisa MIMURA, Keiko IKEDA, Mitsunori NISHIDE, Masanori ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1195-1199
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    A methanolic solution of trans-p-coumaric acid was exposed to ultraviolet radiation and a mixture solution of the trans and cis isomers was subjected to cellulose column chromatography, eluting with an aqueous 0.1% trifluoroacetic acid solution containing methanol (90:10, v/v). Separation of the trans and cis isomers was achieved. The identity of the cis isomer was confirmed by TLC, HPLC, and NMR. Since both the support and eluent are inexpensive, the cis isomers can be obtained economically on both the laboratory and industrial scales.

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  • Zhen CHEN, Liqing ZANG, Yue WU, Hiroko NAKAYAMA, Yasuhito SHIMADA, Roj ...
    Type: Original Papers
    2018 Volume 34 Issue 10 Pages 1201-1208
    Published: October 10, 2018
    Released: October 10, 2018
    [Advance publication] Released: August 10, 2018
    JOURNALS FREE ACCESS

    Type 2 diabetes mellitus is a serious metabolic disorder in the world. Oxidative stress, as a key role on the pathogenesis of diabetes, also results in the oxidation of phospholipids. However, studies on phospholipid oxidation in diabetes, especially directly focusing on oxidized and degraded phospholipid species, are quite limited. In this study, phospholipid profiles of diabetic zebrafish plasma were characterized by LC-HRMS and MS/MS, and the total amounts of each lipid class were compared. Furthermore, the key molecular species as biomarkers in distinguishing control and diabetic samples were investigated by orthogonal partial least squares discriminant analysis. Among the identified 114 phospholipid species in total, there were 11 hydroperoxides, 7 aldehydes, and 19 lysophospholipids found significantly elevated along with the increasing blood glucose, which were known as oxidation or degradation products. Furthermore, lysophosphatidylcholine 20:5 and lysophosphatidylcholine 22:6 were assessed as potential biomarkers in diabetic zebrafish. The current work would not only help to gain further insights into diabetes, but also contribute to find new clinical parameters for the screening of the promising antioxidant agents for its therapies.

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Notes
  • Xiaomin LI, Hiroshi KUROKI, Takashi FUNATSU, Makoto TSUNODA
    Type: Notes
    2018 Volume 34 Issue 10 Pages 1209-1212
    Published: October 10, 2018
    Released: October 10, 2018
    JOURNALS FREE ACCESS

    Recent studies have shown that pillar array columns enable fast and quantitative analysis of amino acids. However, hydrophilic amino acids still cannot be retained on pillar array columns since they have limited retention ability. Ion-pairing liquid chromatography is a promising means of increasing analyte retention. In this study, the effects of ion-pairing reagents on the retention of eight hydrophilic amino acids (histidine, asparagine, glutamine, serine, arginine, aspartic acid, glycine, and glutamic acid) derivatized with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) under reversed-phase conditions on a conventional ODS column were studied. Among the ion-pairing reagents investigated, tetraheptylammonium bromide proved to be the most effective for increasing analyte retention. With a mobile phase consisting of 20 mM citrate buffer (pH 6.3)–acetonitrile (100:40, v/v) and 2 mM tetraheptylammonium bromide, the retention times of the eight NBD-amino acids—except NBD-arginine—were longer than 19.4 min, which was the retention time of NBD-valine when eluted without an ion-pairing reagent. As NBD-valine was well retained on pillar array columns, the chromatographic conditions may thus be applied in the analysis of hydrophilic amino acids using pillar array columns.

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