The electrorotation (ROT) rates of K562 cells accompanied by erythroid differentiation were estimated to identify the differentiation status by using a novel electrorotation device with a microwell arranged on polynomial electrodes. Successive estimations of individual cells were achieved by sequential manipulations which involve trapping of the cell by positive dielectrophoresis (DEP), rotating by ROT, and removing by negative DEP. The ROT rate increased with the differentiation of K562 cells, because the cytoplasm conductivity would increase with an increase of the concentration of iron ions to produce hemoglobin. The ROT rate could be utilized to estimate the stage of cell differentiation without labeling.

Bioluminescence (BL) is an excellent optical readout platform that has great potential to be utilized in various bioassays and molecular imaging. The advantages of BL-based bioassays include the long dynamic range, minimal background, high signal-to-noise ratios, biocompatibility for use in cell-based assays, no need of external light source for excitation, simplicity in the measurement system, and versatility in the assay design. The recent intensive research in BL has greatly diversified the available luciferase–luciferin systems in the bioassay toolbox. However, the wide variety does not promise their successful utilization in various bioassays as new tools. This is mainly due to complexity and confusion with the diversity, and the unavailability of defined standards. This review is intended to provide an overview of recent basic developments and applications in BL studies, and showcases the bioanalytical utilities. We hope that this review can be used as an instant reference on BL and provides useful guidance for readers in narrowing down their potential options in their own assay designs.

Cell analysis is of great significance for the exploration of human diseases and health. However, there are not many techniques for high-throughput cell analysis in the simulated cell microenvironment. The high designability of the microfluidic chip enables multiple kinds of cells to be co-cultured on the chip, with other functions such as sample preprocessing and cell manipulation. Mass spectrometry (MS) can detect a large number of biomolecules without labelling. Therefore, the application of the microfluidic chip coupled with MS has represented a major branch of cell analysis over the past decades. Here, we concisely introduce various microfluidic devices coupled with MS used for cell analysis. The main functions of microfluidic devices are described first, followed by introductions of different interfaces with different types of MS. Then, their various applications in cell analysis are highlighted, with an emphasis on cell metabolism, drug screening, and signal transduction. Current limitations and prospective trends of microfluidics coupled with MS are discussed at the end.

N-Benzylquininium chloride is a versatile functional monomer with quinoline and benzyl groups, which is beneficial for reversed-phase chromatography. In this study, a novel monolithic column with reversed-phase mode was synthesized using N-benzylquininium chloride as the monomer and 3-(acryloyloxy)-2-hydroxypropyl methacrylate as the cross-linker in a binary porogenic solvent consisting of PEG 400 and a 0.05 M sodium hydroxide aqueous solution. The alkaline solution were found to be useful for the improvement of the mechanical stability of the porous monoliths. The monolithic column showed excellent reversed-phase selectivity and various compounds, such as alkylbenzenes, phenols and polycyclic aromatic hydrocarbons, were separated successfully. The highest column efficiency was 1.75 × 10⁵ N m⁻¹. The relative standard deviations of the migration time for thiourea and four alkylbenzenes were all less than 5.0%, which indicates the monolithic column has good stability. The application of the monolithic column for the analysis of polycyclic aromatic hydrocarbons in spiked lake water samples illustrated its great potential for practical application.

A convenient and uncomplicated scheme has been projected for the quantitative determination of essential diamines putrescine (PUT) and cadaverine (CAD) via sodium dodecyl sulfate protected silver nanoparticles (SDS-AgNPs). This scheme is based on the chemical interaction of a SDS-AgNPs probe with PUT and CAD, leading to a color change from yellow to red or reddish brown. The interaction was investigated through different techniques such as using a UV-visible spectrophotometer, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), dynamic light scattering spectroscopy (DLS) and the zeta potential. Both amines possess a close resemblance in structure (except for the addition of one more methylene group in CAD), and no any distinguishable color change was noted. However, the maximum absorption band at 580 and 600 nm was demonstrated for PUT and CAD correspondingly. The methodical response was observed at absorption ratios of 580/410 and 600/410 nm, with the linear regression within 4 – 12 and 6 – 14 μg/mL for PUT and CAD. The detection limits calculated for both the diamines PUT and CAD were 0.333 and 1.638 μg/mL. The scheme was successfully applied for determinations in biological samples, including spiked blood plasma and urine. Putrescine exhibited % recovery within 95.717 – 105.200%, while cadaverine was within 95.940 – 105.109%, respectively. The scheme was reproducible and precise with inter-day RSD (n = 5) within 1.126, 0.018% and the intraday RSD (n = 5) was within 0.005, 0.002% for PUT and CAD, respectively.

Chiral enantiomer recognition is important but facing tough challenges in the direct quantitative determination for complex samples. In this work, via chosing nitrogen-doped silicon quantum dots (N-SiQD) as optical nanoprobe and constructing N-SiQD/silver (N-SiQD/Ag NPs) complex, β-D-GOx as model enzyme and glucose enantiomers as analytes, a fluorescent and colorimetric dual-signal chiral sensing strategy was proposed herein for chiral recognition based on specific enzyme-catalyzed reaction. N-SiQD can exhibit intense fluorescence, while it can be quenched by Ag NPs owing to the formation of N-SiQD/Ag NPs. In the presence of glucose isomer, D-glucose is catalytically hydrolyzed by β-D-GOx to form H₂O₂ owing to the specific enzyme catalyzed reaction between D-glucose and β-D-GOx, and H₂O₂ can etch Ag NPs from the N-SiQD/Ag NPs probe to change the solution color from brown to colorless and restore the N-SiQD fluorescence; while these phenomena cannot be caused by L-glucose, a dual-signal sensing method was thus constructed for recognizing glucose enantiomers. It is believed that the chiral enantiomers recognition strategy via enzyme catalysis has great application for selective and quantificational detection of enantiomers in the complex sample system.

A BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) based pioneering sensing material (HL^Py) having 2-amino pyridine as receptor was synthesized and used for the selective detection of Hg²⁺ ions. The synthesized HL^Py features a high affinity towards Hg²⁺ (k_a = 2.04 × 10⁵ M⁻¹), accompanied by effective quenching of fluorescence in DMF:H₂O (1:9 v/v, 10 mM HEPES buffer, pH 7.4) with 54 nM limit of detection (LOD). The emission titration experiments (Job’s plot) in the presence of varying mole-fraction of Hg²⁺ ions reveals the formation of non-fluorescent 2:1 coordination complex [Hg(L^Py)₂]. The resulting non-fluorescent [Hg(L^Py)₂] was thoroughly characterized using various spectroscopic techniques and analyses. Interestingly, the non-fluorescent complex [Hg(L^Py)₂] is able to specifically respond towards Cys over other biothiols and amino acids through a reversible de-complexation mechanism. As a result, the remarkable recovery of the fluorescence can be observed. The limit of detection (LOD) for Cys detection is estimated to be 29 nM in DMF:H₂O (1:9 v/v, 10 mM HEPES buffer, pH 8.0). The reversibility and reusability of [Hg(L^Py)₂] were achieved by the sequential addition of Cys and Hg²⁺ ions up to five cycles. Moreover, the removal of Hg²⁺ ions up to 89% from aqueous samples using HL^Py was successfully demonstrated.

In this work, a new chemiluminescence (CL) system of Co-Fe prussian blue analogs nanocubes (Co-Fe PBA NCs) that can catalyze luminol to produce strong CL in the absence of H₂O₂ was established. Co-Fe PBA NCs have the property of oxidase-like activity, and it can catalyze the generation of active oxygen radicals in a dissolved oxygen system. Since caffeic acid (CA) can remove reactive oxygen species in the system, a sensitive detection method for CA on a paper-based chip was developed. Under the optimal conditions, this method showed a good linear response to CA in the range of 10 – 800 ng mL⁻¹ with a limit of 3 ng mL⁻¹. The proposed method had been used for the determination of CA in tea samples. The results may open a new avenue for the catalytic property on luminol CL system without extra oxidants.

Leisure dried tofu is a kind of small packaged food which is popular with consumers in China. However, during the storage of leisure dried tofu, moisture and fat may be lost and deteriorate. For their own benefit, bad business operators might forge or mark the production date and shelf life. Therefore, it is necessary to explore a method to determine simultaneously the moisture, fat content, and storage time of leisure dried tofu. Samples were measured for obtaining transverse relaxation data by using low-field nuclear magnetic resonance (LF-NMR) spectrometer. The experimental data were analyzed and modeled by methods including partial least squares (PLS) or back-propagation artificial neural network (BP-ANN). The results show that the models can be used to predict the moisture, fat content, and storage time rapidly, nondestructively, accurately, and simultaneously. Furthermore, in order to explore the changes of nutrients in leisure dried tofu with the storage time, the storage dynamics of moisture and fat was considered by a using corresponding calibration model.

Radiation-sensitive biomolecules are highly significant for studying biological effects of radiation and developing ionizing radiation detectors based on biomolecules. In this work, we selected hypoxanthine phosphoribosyl transferase gene fragments sensitive to gamma-ray irradiation as a sensing element for radiation detection. The end was modified with thiol groups. The thiol-modified oligonucleotide sequences were coupled to the surface of gold nanoparticles by Au–S covalent bonds. The DNA attached to the surface of gold nanoparticles forms a DNA-AuNPs assembly through base pairing. The assembly was irradiated by gamma rays. And its response to radiation was studied with ultraviolet-visible spectroscopy and surface-enhanced Raman scattering (SERS) spectroscopy techniques. SERS spectroscopy and ultraviolet spectroscopy can detect the response of the DNA-AuNPs assembly to gamma-ray irradiation below 100 and 100 – 250 Gy, respectively. The results indicated that it was feasible to develop a new approach of gamma-ray detectors using biomolecular assemblies of gold nanoparticles.

This paper describes a method based on surface enhanced Raman spectroscopy (SERS) technology for rapid detection of dezocine in urine and serum. Firstly, an Ag colloid substrate was prepared and characterized. Then the Raman characteristic peaks of dezocine were assigned from both theoretical and experimental aspects. Finally, the Raman peak at 661 cm⁻¹ was selected as its characteristic peak to perform SERS detection on dezocine in urine and serum, and the detection limits of dezocine in urine and serum were determined. The relationships between the characteristic peak intensity and the concentration of dezocine in urine and serum were fitted and the recovery rates were calculated. This rapid, accurate and non-destructive method establishes a good foundation for rapid on-site detection of dezocine in biological samples.

A direct sampling hydride generation (HG) system based on modified gas liquid separator (GLS) coupled with in situ dielectric barrier discharge (DBD) is first rendered to detect lead in blood samples. Herein, a triple-layer coaxial quartz tube was employed as DBD trap (DBDT) to replace the original atomizer of atomic fluorescence spectrometry (AFS) to satisfy the in situ preconcentration. After 40-fold dilution, foams generated from protein in a blood sample can be eliminated via the double-GLS set; and lead in a blood sample were generated as plumbane under 3.5% HNO₃ (v:v) and 30 g/L NaOH with 8 g/L KBH₄, 10 g/L H₃BO₃, and 5 g/L K₃[Fe(CN)₆]. Then, lead analyte was trapped on the DBD quartz surface by 9 kV discharging at 50 mL/min air; and subsequently released by 12 kV discharging at 110 mL/min H₂. The absolute detection limit (LOD) for Pb was 8 pg (injection volume = 2 mL), and the linearity (R² > 0.997) range was 0.05 – 50 μg/L. The results were in good agreement with that of blood certified reference materials (CRM), and spiked recoveries for real blood samples were 95 – 104% within a relative standard deviation of 5% (RSD). Via gas phase enrichment, the established method improved analytical sensitivity (peak height) by 8 times. The entire analysis time including blood sample preparation can be kept to within 10 min. The combination of modified GLS and DBDT can facilitate the quickness, accuracy, and sensitivity, revealing a promising future for monitoring lead in blood to protect humans, especially children’s health.

Legally regulated synthetic cannabinoids (SCs) are continuously being created by making minor positional modifications to pre-existing analogs; thus, compounds with minor structural differences must be isolated and identified accurately. For iodo-benzoylindole derivatives of SCs, only specific isomers are currently the target of legal control, and it is necessary to establish an analytical method for accurately identifying positional isomers. In this study, we synthesized a series of 57 designer drugs and developed a screening method for identifying halogen positional isomers on the phenyl ring of benzoylindole derivative SCs in serum. Analytical methods using the Discovery F5 pentafluorophenyl column gave the best selectivity and retention of the positional isomer analytes. Some of the meta and para iodo-substituted SCs were eluted at similar retention times and were difficult to separate by liquid chromatography (LC). However, they were identified via the relative abundance of the two product ions in the collision-induced dissociation reaction using LC-hybrid quadrupole/orbitrap high-resolution mass spectrometry. Our synthesized halogen-substituted positional isomer SC library and method for differentiating positional isomers of halogenated benzoylindole SC derivatives could provide an indispensable analysis tool for identifying illegal drugs in serum of drug users.

Cobalt-nickel alloy thin-films were prepared by electrodepositing on Au-coated Al₂O₃ substrate from aqueous solutions of metal-salts, and applied as a potentiometric hydrogen-phosphate ion sensor. A doping of 20 mol% nickel in cobalt contributed to enhancing hydrogen-phosphate ion sensing performances, i.e., the sensing range and response time were drastically improved. The Co₈₀Ni₂₀ thin-film electrode showed good potentiometric response to hydrogen-phosphate ion between 1.0 × 10⁻⁵ and 1.0 × 10⁻³ M with a slope of –59 mV/decade and high anion selectivity. The 90% response time to 1 mM H₂PO₄⁻ was as short as 15 s at pH 5.0, 30°C. A mixed potential sensing mechanism could be proposed on the basis of the results.

Ifosfamide (IF), cyclophosphamide (CP), and bendamustine (BD) are widely used anticancer drugs. These drugs have slight volatility; therefore, medical-staff exposure is of concern in the medical field. However, an accurate and quantitative detection method of these volatile drugs in air has not been reported. In this study, we developed the quantitative extraction and detection method of these volatile anticancer drugs in air. For the extraction of analytes, a solid-phase extraction-type collection device packed with styrene-divinylbenzene polymer particles was used. The extracted analytes were quantitatively eluted with 5 mL of ethanol, and the solution was concentrated to 100 μL with nitrogen purging. The analytes were analyzed using gas chromatography–mass spectrometry (GC-MS). The limit of detection of the proposed method for IF and CP was 0.017 and 0.033 ng L⁻¹, respectively in air at an air sampling volume of 300 L. IF and CP showed slight volatility, whereas BD was not detected in GC-MS due to its lower volatility. The spiked recoveries of IF and CP in the proposed method were within the range of 95.5 to 101%. Finally, the proposed method was applied to determine the exposure of IF and CP during the dispensing of CP within a hospital dispensary room. The investigated volatile anticancer drugs were not detected in real air samples, indicating that the protection measures employed are sufficient.

Nanomolar concentrations of NH₂OH in natural water sources were determined using an Fe³⁺ oxidation method. A pH of 2.35 – 2.50 was used, which was adjusted by adding a chloroacetate buffer. Equal amounts (1.0 mL) of the chloroacetate solution and ferric chloride solution were added to the water sample (70 mL) to oxidize NH₂OH to N₂O. The resulting N₂O in the sample water was then quantified by headspace analysis using a gas chromatograph with an electron-capture detector (ECD), where a limit of detection of 0.2 μgN L⁻¹ (14 nmol L⁻¹) was achieved. This method was successfully applied to samples of freshwater, brackish water, and seawater, and despite the various salinities no interfering substances were observed. Furthermore, NH₂OH was successfully detected in samples collected from the Hii River and Lakes Shinji and Nakaumi (Shimane Prefecture, Japan). In addition, the proposed method was also applicable to samples rich in organic substance derived from phytoplankton.

This paper describes the determination of Pb and Cu with a Nafion-modified glassy carbon electrode and MnCo₂O₄ nanoparticles as working electrode for anodic stripping voltammetry. Pb and Cu were accumulated in HCl/KCl (0.1 mol dm⁻³) at a potential of –1.4 V (vs. Ag/AgCl electrode) for 480 s, followed by a linear sweep anodic stripping voltammetry (ASV) scan from –1.0 to +0.5 V. Under optimum conditions, the calibration curves were linear in the range of 0.01 – 8 and 0.01 – 5 mg dm⁻³ for Pb and Cu, respectively. Effect of sample dilution, accumulation time and potential were optimized. A study of interfering substances was performed. A significant increase in current was obtained at the modified electrode in comparison with the bare glassy carbon electrode. The modified electrode was successfully applied for determination of Pb and Cu in wine samples after a simple preparation procedure. Pb and Cu content in wine was used for estimation of the target hazard quotient (THQ) values for minimal and maximal levels of the metals.

The partition efficiency of the double-spaced coil for eccentric and toroidal coils on countercurrent chromatographic separation of proteins was evaluated using the small-scale cross-axis coil planet centrifuge (CPC) equipped with circular and elliptic cylindrical columns. Standard cytochrome c, myoglobin and lysozyme samples were used for separation with the 12.5% (w/w) polyethylene glycol 1000 and 12.5% (w/w) dibasic potassium phosphate system. In the circular column, the double-spaced eccentric coil yielded better peak resolution than the double-spaced toroidal coil, and the double-spaced eccentric coil yielded better peak resolution than the single-spaced eccentric coil. In the elliptic column, the double-spaced eccentric coil also produced better peak resolution than the double-spaced toroidal coil, but the single-spaced eccentric coil yielded better peak resolution than the double-spaced eccentric coil. The overall results indicated that the double-spaced eccentric coil for the circular column and the single-spaced eccentric coil for the elliptic column yielded better protein separation using the small-scale cross-axis CPC with aqueous two-phase solvent systems.

This paper investigated two-dimensional spatial and temporal images of a copper emission line in laser-induced breakdown spectroscopy (LIBS), in order to clarify the excitation/de-excitation processes occurring in a laser-induced plasma. The measurements were carried out under different plasma gases (argon, krypton, helium, and nitrogen), pressure levels (100 – 900 Pa) and delay times (100 – 1000 ns) with the aim of monitoring their effects on the behavior of the copper emission. Depending on the plasma gas type and the pressure level, large differences were found in the plasma shape and temporal intensity evolution of the copper emission profile. Namely, krypton produced the most compact plasma emitting larger intensities, compared to argon and helium, and an increase in the gas pressure made these plasmas to shrink, which could be related principally to the stopping power of the applied gases. Through temporally resolved analysis, the delay profiles could be obtained for each plasma gas, indicating that the helium plasma disappeared more rapidly than the argon and krypton plasmas. It was suggested that the variations in the emission intensity would be determined by interactions between gas particles and highly energetic particles in the plasma breakdown as well as interactions between excited gas particles and copper species during plasma expansion. These insights could prove to be useful in the understanding of the background of LIBS as well as the optimization of its practical applications.

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.

The separation properties of arsenic species was investigated using HPLC-ICP-MS with several commercially available fluorocarbon stationary phases and no ion-pair reagents in HPLC. One pentafluorophenyl column showed the highest potential for the separation of a larger number of arsenic species when using simple acid-based mobile phases. After modification of the operational parameters in HPLC, the speciation analysis of 13 representative arsenic species: arsenite, arsenate, methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, tetramethylarsonium, arsenobetaine, arsenocholine, thio-dimethylarsinic acid, oxo-arsenosugar-glycerol, oxo-arsenosugar-phosphate, oxo-arsenosugar-sulfonate, and oxo-arsenosugar-sulfate, was achieved by HPLC-ICP-MS with the column along with a mobile phase of 0.05% heptafluorobutyric acid–methanol (99:1, volume per volume).

Chromium oxide(VI), (Cr(VI)) has been used in gas detector tubes as an indicator to detect alcohols. However, it is toxic and regulated to prevent environmental pollution. In this report, potassium manganate(VII) was chosen instead of Cr(VI). A samples of 100 mL of ethanol, methanol and 2-propanol vapors were passed through a gas detector tube with an aspirating pump. Sampling time was 3 min. The stain length on the tube was in the range of 20 – 300 ppm. A novel detector tube for alcohols was developed without Cr(VI).