Why does the adsorption and concentration of inorganic chemical species proceed at aqueous–solid interfaces? In this review paper, we discuss the use of X-ray chemical state analysis to elucidate the intrinsic adsorption mechanism. Based on the chemical states of the species adsorbed to solids as determined by X-ray chemical state analysis, possible adsorption mechanisms are discussed. The driving forces of adsorption are represented by the Gibbs free energy change (ΔG_chem = ΔG_chem,1 + ΔG_chem,2) resulting from the formation of covalent bonds between metal ions (M) in metal oxides or hydroxides and adsorbed species (X) (M–O–X bond, ΔG_chem,1) and the formation of new phases consisting of M and X (ΔG_chem,2). The concept of ΔG_chem,2 is proposed based on the experimental results from chemical state analyses. As examples, the following investigations are discussed in this review paper: the formation of mullite precursors by the adsorption of monosilicic acid to Al(OH)₃, the spontaneous reduction of Au(III) to Au(0) by adsorption of Au(III) to Al(OH)₃, MnO₂ and Ni(OH)₂ and the mechanism of concentration of Co²⁺, Tl⁺, Pb²⁺, Pt²⁺, Au⁺, and Pd²⁺ in marine ferromanganese crusts.

For materials development with high-level structural regulations, the emerging concept of nanoarchitectonics has been proposed. Analytical sciences, including sensing/detection, sensors, and related device construction, are active targets of the nanoarchitectonics approach. This review article focuses on the two features of interface and nanostructures are especially focused to discuss nanoarchitectonics for analytical science. Especially, two selected topics, (i) analyses on molecular sensing at interfaces and (ii) sensors using self-assembled supramolecular nanostructures, are exemplified in this review article. In addition to recent general examples, specific molecular recognition at the air–water interface and fabrication of sensing materials upon self-assembly of fullerene units are discussed. Descriptions of these examples indicate that nanoarchitectonics and analytical science share common benefits, and therefore, developments in both research fields should lead to synergies.

In recent years, more and more research is being conducted on microRNAs and their involvement in the regulation of autophagy phagocytosis which is closely related to tumor growth. MicroRNA-21 is a kind of small RNA that can regulate gene expression and plays a significant role in autophagy of tumor cells. But the detection of microRNAs had always been a problem in the field of biological analysis. In this study, we designed a new fluorescent sensor for the detection of miRNA-21. The sensor was based on the successful signal reporting by E36-encapsulated vesicles and the specific interaction between E36 and miRNA-21. In the presence of miRNA, the E36/miRNA-21 complex formed and served as a donor molecule inside the acceptor PDA vesicles to amplify the fluorescence through FRET. Additionally, the sensor was applied to detect miRNA-21 in complex biological samples with satisfactory results.

A facile and one-step colorimetric assay is described for the determination of glutathione (GSH). It is based on the use of manganese dioxide-decorated magnetic (Fe₃O₄@MnO₂) nanocomposite that was prepared by an in-situ redox reaction. It exhibits oxidase-mimicking activity and can catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) without H₂O₂to form a blue colored product (oxTMB) with an absorption maximum at 651 nm. Once GSH is introduced, the component of MnO₂ can be rapidly reduced to Mn²⁺ ions, which leads to inhibit the formation of oxTMB. Based on these findings, a one-step colorimetric assay was developed for the detection GSH in the range of 0.2 to 25 μM with a low detection limit of 0.2 μM without using any procedures of separation and washing. Importantly, the proposed approach is also used to accurately evaluate the intracellular GSH levels. In our perception, the assay is rapid, sensitive and specific.

We have developed a novel FRET-based assay to monitor protein kinase activity using quantum dots (QDs) and fluorophore-labeled substrate peptides. To develop a FRET-based protein kinase assay, it is important to consider the phosphate group recognition strategy and to ensure that the FRET pairs are close enough because the FRET efficiency is highly dependent on the distance between the FRET pairs. Here, we incorporated a phos-tag, which captures phosphate groups strongly and selectively, into a protein kinase assay to recognize phosphorylation. Our detection system was composed of phos-tag-modified QDs and Cy5-labeled substrate peptides. Because the phos-tags capture phosphate groups by forming dinuclear complexes, the Cy5-labeled substrate peptides are captured by the phos-tags on the QD surface upon protein kinase-mediated phosphorylation, which induces FRET from the QDs to Cy5 because of the approximation of Cy5 to the QDs. On the basis of the difference of this FRET efficiency, we successfully measured protein kinase A activity, which demonstrated the feasibility of our assay.

Hydrogen peroxide (H₂O₂), an important representatives of reactive oxygen species, its aberrant expression is related to many diseases, including cancers. Therefore, it is very significant to design a reliable method for the real-time detection of endogenous H₂O₂. Herein, we describe preparing a poly (azure I)/crumpled graphene (cGN) modified electrode by an electro-polymerization method. The results showed that this electrode presented obvious electrocatalytic effect on the reduction of H₂O₂. Amperometric method was employed to monitor H₂O₂, and the amperometric response exhibited a good linear relationship with its concentration in the range of 8.0 × 10⁻⁶ – 1.25 × 10⁻³ mol/L; the detection limit reached to 6.7 × 10⁻⁷ mol/L (S/N = 3). Furthermore, this modified also displayed good selectivity, long-term stability and a high anti-interference ability. Excitingly, the established method could be successfully used to detect H₂O₂ in human serum samples, and measured H₂O₂ secreted from living MCF-7 cells. It could have potential use in cancer diagnosis.

Tube radial distribution chromatography based on the tube radial distribution flow, or annular flow, in an open-tubular capillary has been reported, where the annular flow is created through phase-separation multiphase flow. We have proposed the first-ever procedure for consecutive sample injection analysis using chromatography. In basic terms, a commercially available HPLC system could be used with a sample injector (0.2 μL volume) and a fused-silica capillary tube (250 cm long) as a separation column instead of a normal packed one, while the built-in detection cell was replaced by improved on-capillary detection. A ternary mixed solution of water/acetonitrile/ethyl acetate (3:8:4 volume ratio) was delivered into the capillary tube as an eluent at a flow rate of 2.0 μL min⁻¹. Model sample solutions of 1-naphthol and 2,6-naphthalenedisulfonic acid were consecutively analyzed by the present chromatography with a processing rate of 6 samples per hour. Simple and rapid consecutive analysis could be performed because washing and initialization of the separation tube was no longer necessary. The obtained results provide clues to developing new methodologies which combine features of both chromatography (separation) and the flow injection method (consecutive analysis).

This paper describes that fluorous ethers, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether and 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether, can be used for a non-aqueous medium in electrochemistry at a liquid | liquid interface. These solvents dissolved a high concentration of tetraalkylammonium salts with highly-fluorinated anions, such as bis(nonafluorobutanesulfonyl)imide and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ions, and the solution had a high conductivity. The fluorous ether | water interfaces exhibited a substantial polarizable potential window, and various ions, including tetraphenylarsonium and tetraphenylborate ions, gave a reversible voltammetric wave due to their ion transfer across the interfaces. Using the tetraphenylarsonium-tetraphenylborate assumption, the formal potentials for the ion transfer and the formal Gibbs energies of ion transfer from the ethers to water were estimated. The Gibbs energies were close to those from a previously reported fluorous solvent, 1,1,1,2,3,4,4,5,5,5-decafluoropentane; the fluorous ethers also exhibited a higher affinity for fluorinated ions. Because of a lower volatility, the fluorous ethers would be more advantageously used in two-phase electrochemistry, particularly concerning analytical purposes.

This study describes the development of a new stable isotope labeling method by carbon-13 in bacteria culture (SILCB) for the analysis of residual antibiotics via liquid chromatography with tandem mass spectrometry (LC-MS/MS). Stable isotope dilution (SID) LC-MS/MS with QuEChERS was employed to determine avermectin, particularly avermectin B1a (AV-a) and B1b (AV-b), based on completely ¹³C-labeled internal standards (¹³C-ISs) obtained from the SILCB. Our SILCB was developed from an optimal inorganic medium using ¹³C₆-glucose for Streptomyces avermitilis (14893 strain). A rough extract containing ¹³C-ISs was purified via high-speed countercurrent chromatography with a volatile two-phase solvent system composed of n-hexane/ethyl acetate/methanol/0.5% formic acid in water (7/3/5/5/, V/V). The purified ¹³C-ISs were evaluated to confirm the presence of completely ¹³C-labeled ions with m/z 938 > 326 and m/z 923 > 309 for AV-a and AV-b, respectively. The QuEChERS approach with the ¹³C-ISs procedure achieved acceptable recovery rates in beef meat samples of 99.5 – 100.0% (RSD < 2.0%, n = 6). For the analysis of residual antibiotics in foodstuffs by SID-LC-MS/MS and QuEChERS, the SILCB represents a significant improvement over previous methods suffering from cumbersome sample preparation and matrix effects.

Physical and chemical properties of a redox protein adsorbed to different interfaces of a multilayer immunoassay assembly were studied using a single-mode, electro-active, integrated optical waveguide (SM-EA-IOW) platform. For each interface of the immunoassay assembly (indium tin oxide, 3-aminopropyl triethoxysilane, recombinant protein G, antibody, and bovine serum albumin) the surface density, the adsorption kinetics, and the electron-transfer rate of bound species of the redox-active cytochrome c (Cyt-C) protein were accurately quantified at very low surface concentrations of redox species (from 0.4 to 4% of a full monolayer) using a highly sensitive optical impedance spectroscopy (OIS) technique based on measurements obtained with the SM-EA-IOW platform. The technique is shown here to provide quantitative insights into an important immunoassay assembly for characterization and understanding of the mechanisms of electron transfer rate, the affinity strength of molecular binding, and the associated bio-selectivity. Such methodology and acquired knowledge are crucial for the development of novel and advanced immuno-biosensors.

Non-destructive observations of cross-sectional shapes of acrylic single fibers using X-ray computed tomography (CT) were performed. A commercial X-ray CT apparatus (Rigaku nano3DX) was employed because of its micrometer-scale spatial resolution and remarkable image contrast for soft matter. We assessed two types of sample support, a paraffin strip and a nylon string, for single fiber samples in terms of easy handling and sample recovery. Fixed individual single fibers were loaded into a narrow polyimide tube in both cases, and the tube ensured that the sample remained in the field of view during the CT measurements. In both cases, the cross-sectional shapes of individual single fibers could be distinguished, with a circular shape for one sample and a triangular shape for the other. However, the support using a nylon string was found to be more suitable for further analysis. The cross-sectional profile of the obtained tomographic image showed a clear difference between polyimide and nylon. The intensity ratio or the image contrast corresponded to that of the local densities. It was also found that the effect of the artifact appeared at around the boundaries of the objects, but the local density could still be utilized for examining individual single fibers.

In the current work a uniform morphological Ag nanoparticles (Ag NPs) were prepared with ascorbic acid as a reducing agent and citrate as a stabilizer. The surface of Ag NPs modified by crystal violet (CV) and potassium iodide (KI) was used as an aggregation agent to obtain CV modified Ag NPs (CV-Ag NPs) probes for detecting mercury ions. The mercury ions could be reduced to mercury molecules by citrate, and then deposited on the surface of Ag NPs, leading to the separation of CV molecules from the surface of Ag NPs. Therefore, the SERS signal intensity of CV decreased with the increase of the Hg²⁺ concentration and the concentration of Hg²⁺ was in the range of 1 × 10⁻¹¹ to 1 × 10⁻⁵ M. Taking the change of the characteristic peak intensity of CV at 913 cm⁻¹ as a reference, the SERS spectrum intensity of CV has a linear relationship with the Hg²⁺ concentration. The equation is y = –333.55x + 1343.05, where the linear correlation coefficient is R² = 0.980, and the recovery rate is between 84.20 to 105.60%. Finally, the CV-Ag NPs probe was used to quickly detect soluble mercury in cinnabar. Compared with the conventional large-scale instrument detection method, this simple and fast method, can be applied for rapid detection of soluble mercury, and has a certain significance for concerning the research of mineral medicine processing mechanism.

Saikosaponin a and saikosaponin d are used as chemical standards for the quality evaluation of Bupleurum chinense DC. by the high-performance liquid chromatography method in current Chinese Pharmacopoeia. However, other saikosaponins, such as saikosaponin c and saikosaponin b₂, also possess pharmaceutical activity, but are not used as chemical standards. In this study, a quantitative proton nuclear magnetic resonance (¹H NMR) method was developed to determine the total mass percentage (mg/g) of SSa, SSb₁, SSb₂ and SSd in B. chinense DC., using the H-24 (δ_H 0.71) signal. Furthermore, the molality (mol/kg) of type I saikosaponins (epoxy-ether structure) was also determined by quantitative ¹H NMR in the area of H-11 (δ_H 5.95) for a more accurate quality evaluation. Validation of the method confirmed that it has acceptable selectivity, precision, stability, and repeatability. The results indicated that this method has the potential to be a reliable method for the quantification of saikosaponins in Bupleurum scorzonerifolium Willd., vinegar baked B. chinense DC. and B. scorzonerifolium Willd., Chaihu Koufuye (oral liquid of Chaihu).

The non-enzymatic electrochemical sensing platform for hydrogen peroxide by using Pt-based nanoparticle was investigated. The characterization of PtNiCo-NPs was done by XRD, TEM, HRTEM, EDS, and XPS. A simple drop-casting technique was used to fabricate the nanomaterial on FTO electrode. The amperometric and cyclic voltammetric results illustrated that PtNiCo-NPs on FTO had excellent electrochemical performance over other mono or bimetallic materials. The catalytic performance for H₂O₂ sensing based on PtNiCo-NPs possessed a wide linear range from 5 μM to 16.5 mM with a low detection limit of 0.37 μM and a good sensitivity of 1374.4 μA mM⁻¹ cm⁻² at a scan rate of 20 mV s⁻¹ (vs. Ag/AgCl). This work presents a new way to produce a ternary nanomaterial for H₂O₂ sensing with excellent electrochemical performance. In addition, the fabricated nanomaterial showed no interferences for common interfering agents, which indicates the high specificity of the sensor. The PtNiCo-NPs have excellent stability and good reproducibility in real samples.

An easy method is presented for producing gold nanoparticles. We show that by performing simultaneous low-temperature heating of a quartz glass substrate on which the dry residue of a 10 μL droplet of an HCl acidic solution of HAuCl₄·4H₂O is deposited and a counter substrate using Peltier devices in a low vacuum produced by a rotary pump, gold nanoparticles with sizes ranging from about twenty to one hundred and several tens of nanometers are produced on the counter substrate. In this study, an application of a gold nanoparticle substrate produced by this method to the sample holder for surface-enhanced Raman scattering analysis is also shown.

A novel extraction method named hydrogen fluoride assisted–glass surface etching based liquid phase microextraction (HF-GSE-LPME) was proposed to determine 4-n-nonylphenol at trace levels by gas chromatography–mass spectrometry (GC-MS). After the evaluation of system analytical performance for the HF-GSE-LPME-GC-MS system, limit of detection (LOD) and limit of quantification (LOQ) values were calculated as 7.1 and 23.8 ng/g, respectively. Enhancement in detection power of the method was determined to be 22 fold when LOD values of the GC-MS and HF-GSE-LPME-GC-MS systems were compared with each other. Applicability and accuracy of the established method were checked by performing spiking experiments. A matrix matching calibration strategy was applied to boost the accuracy of quantification in both matrices, and the percent recovery results obtained for bottled drinking water and dam lake water samples were in the range of 98 – 107 and 90 – 117%, respectively.

A novel electrokinetic filtration device using a plugged hydrogel was developed to directly measure the initial rate of enzyme reactions. In the proposed method, the enzyme reaction proceeded only for a short time when the substrate was passed through a thin layer of enzyme trapped by the hydrogel without any lag times for mixing and detection. In experimental conditions, alkaline phosphatase (enzyme) was filtrated at a cathodic-side interface of the plugged hydrogel by molecular sieving effect, providing the thin enzyme zone whose thickness was approximately 100 μm. When 4-methylumberiferyl phosphate (substrate) was electrokinetically introduced into the device after trapping the enzyme, 4-methylumberiferone (product) was generated by the enzyme reaction for only 1.26 s as the substrate passed through the trapped enzyme zone. As a result, the initial rate of the enzyme reaction could be directly calculated to 31.0 μM/s by simply dividing the concentration of the product by the tunable reaction time. Compared to the initial rate obtained by mixing the enzyme and substrate solutions, the value of the maximum velocity of the enzyme reaction was 30-fold larger than that in the mixing method due to the preconcentration of the enzyme by trapping. The Michaelis–Menten constant in the proposed method was 2.7-fold larger than that in the mixing method, suggesting the variation of changes in the equilibrium of complex formation under the experimental conditions.

Micro X-ray fluorescence (XRF) enables the non-destructive analysis of particle contamination. In this study, we compared the detection sensitivities and the LLD (lower limit of detection) values of micro-metallic particle contaminations on the plastic detected by micro-XRF and confocal micro-XRF. First, to verify the effectiveness of the confocal micro-XRF, we compared the intensities of different shaping copper samples (plate, thin film and particle). The results demonstrated that confocal micro-XRF is more effective than micro-XRF for the detection of micro particles. Second, to compare the SN ratios of different X-ray energies, several micro-metallic particles (Si, Fe, and Cu) set on an acrylic plate were measured by micro-XRF and confocal micro-XRF. It was found that the SN ratios of the confocal micro-XRF when measuring the Si, Fe, and Cu particles were improved to be approximately 14.6, 21.9, and 43.5-times those of the micro-XRF, respectively. It was determined that confocal micro-XRF is more effective for micro-metallic particles in the higher energy region.

The creaming behavior of an oil-in-water (O/W) emulsion was quantitatively evaluated via resonance-enhanced multiphoton ionization time-of-flight mass spectrometry. Styrene O/W emulsions were prepared with initial styrene concentrations of 1 and 4 g/L, and the height at the center of the sample was monitored. A peak area of the molecular ion of styrene was set as the signal intensity, for which a time profile was constructed from a series of mass spectra. As a result, the averaged time profiles showed that the signal intensities increased once and then decreased with the onset of creaming. In addition, in order to fit an experimentally obtained time profile, a modified fit function was proposed. Based on the fit results, the ratios of the increases and decreases in signal intensities were different between the two emulsions—higher in the case of an O/W emulsion with a higher initial oil concentration. On the other hand, the duration of the enhancement of the signal intensity with the onset of creaming was independent of the initial oil concentration. The present method offers the possibility to quantitatively evaluate the creaming behavior of an emulsion without pretreatment, and, therefore, would be useful for confirming the stability and quality assurance of emulsions.

A significant problem encountered in Chinese chives (Allium tuberosum) grown in greenhouses is the reduction in the yield and quality due to symptoms of withered leaf tips. Withered leaf tips of three Chinese chive cultivars were nondestructively analyzed by microbeam synchrotron radiation X-ray fluorescence (μ-SR-XRF) imaging. Dead, wilting, and healthy parts of the leaves exhibited significant variations in the mineral composition. The Ca/K X-ray intensity ratios were significantly increased with the degree of withering.

Although benzofuran-2-boronic acid hardly emits fluorescence, it can be rapidly converted to a highly fluorescent benzofuran dimer after mixing with a palladium catalyst and amine. We found that a fluorescence enhancement accompanying dimerization was quantitatively promoted upon increasing the concentration of amine. In the present study, we developed a simple fluorescence assay for amines based on the promotive effect. As the result of a fluorescence measurement of the reaction mixture of 19 kinds of typical amines, it was found that tertiary amines including triethylamine (TEA) provided a significant fluorescence enhancement. Finally, the fluorogenic reaction could be applied to develop a high-throughput fluorescent microplate assay for TEA with the limit of detection (blank + 3SD) of 0.091 μM.

An enzyme immunoassay, in which an enzyme (e.g., alkaline phosphatase, ALP) is conjugated with an antibody, is a precise and simple protein detection method. Precise measurements of enzymes at low concentrations allow for ultrasensitive protein detection. The application of a phosphorylated substrate to ALP, followed by using a dephosphorylated substrate in thionicotinamide-adenine dinucleotide cycling, provides a simple and precise quantification of ALP. We describe a protocol for detecting ALP at the zeptomole level using a simple colorimetric method.

In this paper, we report a single-step trypsin inhibitor assay on a microchannel array device immobilizing enzymes and substrates by inkjet printing. The microdevice is composed of a poly(dimethylsiloxane) (PDMS) microchannel array that immobilizes trypsin and fluorescent substrates as reactive reagents at the two bottom corners of a microchannel. Inkjet printers allow simple, accurate, and position-selective immobilization of reagents as nanoliter spots. Therefore, plural reactive reagents, such as enzymes and substrates, can be separately immobilized at different positions in the same microchannel without mixing, and thus allowing for single-step operation by simply introducing a sample solution through capillary action. Furthermore, reproducible fabrication and mass production of the device could be expected. In this study, the efficiency of an acidic solution as a spotting agent for protease immobilization to prevent decrease in the fluorescence intensity was confirmed. Additionally, single-step trypsin inhibitor screening was performed using three inhibitors. Finally, we investigated the storage stability of the device and confirmed that it remained stable for at least 10 days.

Understanding the transport property of Li ions is crucial for improving the performance of Li-ion batteries. To investigate the ion diffusion at high temperatures, we constructed a high-temperature pulsed-field-gradient (PFG) nuclear magnetic resonance (NMR) probe capable of measurements at temperatures >700 K. The accuracy of the sample temperature was confirmed via ⁷⁹Br NMR measurements of KBr. ⁷Li PFG-NMR measurements of Li₂CO₃ were performed at temperatures up to 724 K using the probe. The apparent diffusion coefficient of Li ions in Li₂CO₃ was obtained experimentally.