Search

Inductively coupled plasma-mass spectrometry (ICP-MS) with elemental labeling is a promising strategy for multiplex microRNA (miRNA) analysis. However, it is still challenging for specific analysis of multiple miRNAs with high homology, and the development of multiplex assays is always limited by the complexity of the sequence design. Herein, a simple and direct ICP-MS-based assay was developed for the simultaneous detection of three miRNAs by combining the lanthanide labeling strategy with entropy-driven catalytic (EDC) amplification. Owing to the specificity of EDC for nucleic acid recognition, it is able to differentiate miRNAs with single-base mutation in each EDC circuit. A universal biotin-labeled DNA strand was designed to hybridize with the DNA substrates for three EDC circuits, targeting miRNA-21, miRNA-155, and miRNA-10b, respectively. All the substrates were loaded on the surface of streptavidin magnetic beads. In the presence of target miRNA, the EDC reaction was initiated, and EDC substrates were dissociated, continuously releasing reporter strands that were labeled with lanthanides (Tb/Ho/Lu). After magnetic separation, the supernatant containing the released reporter strands was introduced into an ICP-MS system for simultaneous detection of

A highly sensitive and simple method based on rolling circle amplification (RCA) and single particle inductively coupled plasma mass spectrometry (spICP-MS) was proposed for the homogeneous detection of hepatitis B virus (HBV) deoxyribonucleic acid (DNA). In the presence of target DNA, long ssDNA possessing a large number of repeating sequence units was generated by RCA. DNA-labeled AuNP probes assembled into long chains based on complementary base pairing, further aggregating into large particles. Small Au NPs hardly produced pulse signals in spICP-MS; obvious pulse signals appeared in spICP-MS after the agglomeration of Au NPs caused by the addition of RCA products and spermidine. On the basis of this, the homogeneous detection of target DNA was realized by spICP-MS with high sensitivity. Under optimal conditions, the proposed method exhibited a good linear relationship between the frequency of the pulse signal of Au in spICP-MS and the concentration of target HBV DNA in the range of 10-2000 fmol L

High-throughput single-cell analysis is critical to elucidate the cell heterogeneity. Recently, droplet microchips using oil/gas phases to generate single-cell encapsulated droplets have been combined with inductively coupled plasma-mass spectrometry (ICP-MS) for determination of trace elements in single cells with a throughput of dozens of cells per min. To improve the sample throughput and avoid the oil phase introduced into ICP-MS, herein, a negative magnetophoresis focusing microchip was established and online-coupled to ICP-MS for single-cell analysis. MCF-7 cells in the paramagnetic salt solution were introduced into the designed focusing microchannel, in which they were focused into a single stream under both the magnetic repulsion force and inertial lift force, and then were introduced into ICP-MS for online single-cell analysis. The important parameters including the chip design, the concentration of the paramagnetic salt solution, flow rate, cell density, and dwell time were optimized. Under the optimal conditions, a high sample throughput of 1390 cells min

An amino-functionalized magnetic covalent organic framework composite TpBD-(NH

This work reported a simple and ultrasensitive label-free method for the detection of hepatitis B virus (HBV) DNA by combining hyperbranched rolling circle amplification (HRCA) with dual-mode detection by inductively coupled plasma mass spectrometry (ICP-MS) and fluorescence using ruthenium complex [Ru(bpy)2dppz]2+ (bpy = 2,2'-bipyridine, dppz = dipyrido [3,2-a:2',3'-c] phenazine) as a dual functional probe. An HBV DNA-initiated HRCA system was designed to realize the highly efficient amplification of HBV DNA with the generation of a mass of dsDNA. Also, the [Ru(bpy)2dppz]2+ probe was then added to intercalate into the dsDNA products, resulting in strong fluorescence recovery of the probe for fluorescence detection. Meanwhile, using a biotin-modified primer in HRCA, the dsDNA-[Ru(bpy)2dppz]2+ complexes could be captured by the avidin-coated 96-well plates, and the captured [Ru(bpy)2dppz]2+ probe was later desorbed by acid for ICP-MS detection. The linear range of the proposed method was 3.5-200 amol L-1 and the limit of detection (LOD) was 1 amol L-1 for ICP-MS detection, while the linear range was 20-500 amol L-1 and the LOD was 9.6 amol L-1 for fluorescence detection. The developed method was applied to human serum sample analysis, and the analytical results coincided very well with those obtained by the real-time polymerase chain reaction (PCR) method. The developed dual-mode label-free detection method was ultrasensitive, simple, and accurate, showing great potential for therapeutic monitoring of HBV infection.

The loop heat pipe is a passive high-efficiency two-phase transfer device. To study the effects of the liquid and vapor line lengths on the performance of ethane loop heat pipe (ELHP), a performance test system has been set up based on a pulse tube refrigerator (PTR). The lengths of liquid line (LL) and vapor line (VL) of the ELHP are changed in this test system. The LL length is set as 180 mm, 500 mm, 800 mm, 1100 mm and 1500 mm, respectively, when the VL length is 500 mm. In addition, the VL length is set as 800 mm, 1100 mm, and 1500 mm, respectively, as the LL length is 500 mm. The thermal performances of ELHP including startup performance, thermal resistance and temperature difference are investigated in detail under 170 ~ 240 K temperature regions. The experiment results show that the lengths of LL have an important effect on the startup performance when the heat load (HL) of the ELHP is 0 W. The shorter the LL length is, the easier the startup is at 0 W HL. When the LL length is longer, the ELHP is more stable and the temperature oscillation is smaller. The effect of the VL length on the ELHP startup performance is the same as that of the LL length. Due to the thermophysical properties of ethane, the ELHP in the 240 K temperature region has the best performance.

A novel sulfur-containing functional core–shell magnetic porous organic polymer (Fe3O4@BD-TpMA-S-SH MOP) was synthesized as a magnetic solid-phase extraction (MSPE) sorbent for mercury speciation followed by high-performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) detection. The prepared Fe3O4@BD-TpMA-S-SH MOP possessed rich active adsorption sites (S: 25 wt%), high magnetism (39.2 emu g−1) and high adsorption capacity (636, 656, 649 and 366 mg g−1 for Hg2+, methylmercury (MeHg+), ethylmercury (EtHg+) and phenylmercury (PhHg+), respectively). Under the optimal conditions, the limit of detection (LOD) of the developed MSPE-HPLC-ICP-MS method was 0.43, 0.55, 0.69 and 1.1 ng L−1 for Hg2+, MeHg+, EtHg+ and PhHg+, respectively, with a high enrichment factor (EF) in the range of 346–383-fold. The accuracy of the method was validated, and it was successfully applied for trace/ultratrace mercury speciation in environmental water and fish samples. The developed method has high sensitivity, low LOD, high EF, fast adsorption/desorption dynamics and good matrix resistance ability, showing great applicability in real sample analysis with complex sample matrices.

Quantification of multiple disease-related microRNAs (miRNAs) is of great significance for clinical diagnosis. Based on the simultaneous multiple element detection ability of inductively coupled plasma-mass spectrometry (ICP-MS) and good specificity of multicomponent nucleic acid enzymes (MNAzymes), a novel and simple method based on the MNAzyme amplification strategy and lanthanide labeling coupled with ICP-MS detection was proposed for the sensitive and simultaneous detection of three miRNAs (miRNA-21, miRNA-155, and miRNA-10b). Specifically, a probe consisting of streptavidin-modified magnetic beads (SA-MBs) and three DNA substrates labeled with lanthanide tags (159Tb/165Ho/175Lu) was constructed. In the presence of target miRNAs, three pairs of MNAzymes were assembled where each pair was hybridized with the corresponding miRNA, and then the substrates on the SA-MBs were cleaved by the activated MNAzymes, continuously releasing the fragment with lanthanide tags. The released lanthanide tags in the supernatant were collected after magnetic separation and analyzed by ICP-MS, realizing the simultaneous quantification of multiple miRNAs. The correlation of the lanthanide tag signal with the miRNA concentration fitted well in a linear model in the range of 50-1000 pmol L-1 (miRNA-21) and 50-2000 pmol L-1 (miRNA-155 and miRNA-10b). The limits of detection for three miRNAs were 11-20 pmol L-1, with the relative standard deviations of 2.2-2.7%. The recoveries of target miRNAs in the human serum and HepG-2 cells were in the range of 87.2-111% and 93.3-111%, respectively. Overall, the method is ideal for the simultaneous quantification of multiple miRNAs with advantages of low spectral interference, high sensitivity, good selectivity, and strong resistance to the complex matrix.

Adenosine triphosphate (ATP), as a high-energy phosphate compound that stores and releases energy in living cells, has an irreplaceable role in many physiological processes and maintenance of biological functions, and can be used as an indicator of many diseases. In this work, a composite nanoprobe, silver nanocluster (AgNC) @ molybdenum disulfide (MoS2), was designed to achieve in situ fluorescence imaging and quantitative analysis of intracellular ATP in HeLa cells by fluorescence spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). The probe was constructed based on the adsorption of DNA-AgNCs by MoS2 nanosheets, and the DNA-AgNCs were prepared with the ATP aptamer as a template, whose fluorescence was initially quenched by MoS2. When the probe was incubated into the cells, intracellular ATP recognized the aptamer sequence and caused the DNA-AgNCs to fall off the MoS2 nanosheets, resulting in fluorescence recovery. Here, AgNCs not only acted as a fluorescence label for imaging, but also as an element tag for quantitative analysis of intracellular ATP with the detection of 107Ag by ICP-MS. The ATP in HeLa cells detected by this method was 24.6 ± 1.7 nmol L−1, which was in good agreement with the test result of the ATP test kit (20.4 ± 0.8 nmol L−1). The proposed method has potential application in medical clinical diagnosis and evaluation of the body’s metabolic level via fluorescence imaging and ICP-MS detection of intracellular ATP.

A spiral stir bar was proposed by using stainless steel spring as the extraction phase carrier to avoid the extraction phase friction and increase the amount of extraction phase for improving extraction efficiency. The extraction phase is filled in the cavity of the spring, resulting in a larger amount of the extraction phase than that conventionally coated on glass stir bar or stainless steel wire. Polyaniline-polydimethylsiloxane sol-gel packed spiral stir bar was prepared and evaluated for the extraction of five estrogens. The prepared spiral stir bar presented good extraction efficiency/preparation reproducibility and long lifetime (more than 150 reused times) for target estrogens. Based on it, a method of spiral stir bar sorptive extraction combined with high performance liquid chromatography coupled with ultra-violet detection was developed for the analysis of trace estrogens in environmental and food samples. The detection limit for five estrogens was 0.11-.31 µg/L, with the enrichment factors of 83.0-118-fold (maximal enrichment factor: 200-fold). The reproducibility evaluated with each estrogen of 5 µg/L (n = 5) was 5.8-8.9%. The method was successfully applied for the determination of estrogens in environmental water and animal-derived food samples.

Inductively coupled plasma mass spectrometry (ICP-MS) has emerged as a promising analytical platform for the quantification of biomolecules using elemental tags; however, absolute quantification at extremely low concentrations by ICP-MS without a calibration curve remains challenging. Here, we developed a digital loop-mediated isothermal amplification (LAMP) assay for counting hepatitis B virus (HBV) DNA using single-particle (sp) ICP-MS. The sample and LAMP reagents were mixed and encapsulated in agarose droplets, which were generated by homemade centrifugal droplet generators. The agarose droplets were incubated at 65 °C for amplifying the virus DNA with LAMP primers and then cooled to 4 °C for generating "gel" particles during the temperature-dependent "sol-gel" transition. The LAMP amplicons were intercalated into the agarose particles using polyacrylamide-modified LAMP primers, enabling the labeling of dsDNA with [Ru(bpy)

Exosomes, potential biomarkers for liquid biopsy, provide a promising opportunity for early cancer diagnosis in a noninvasive manner. However, direct analysis of exosomes in complicated biological samples is still challenging. Herein, a cholesterol recognition assay was proposed for detection of exosomes by gold nanoparticles (Au NPs) labeling inductively coupled plasma mass spectrometry. Specifically, exosomes were captured by anti-CD63, and then cholesterol-modified rolling circle amplification product was inserted into the membrane of exosomes for signal amplification. Simultaneously, Au NPs-labelled DNA was prepared for labeling and read-out signal. The proposed method achieved the quantification of the exosome concentration in a range of 10-10

Three porous organic frameworks (POFs) were synthesized by the reaction between phloroglucinol and 1,4-phthalaldehyde, 4,4'-biphenyldialdehyde or tris-(4-formylphenyl) amine; the products are named as POF-a, POF-b and POF-c, respectively. They were used to prepare POFs coated stir bars respectively for the extraction of four carbamate pesticides (CMPs). POF-c coated stir bar exhibited better adsorption performance than POF-a/b coated stir bar and commercial stir bars, probably due to the stronger conjugated structure and hydrophobicity of POF-c, and resultant hydrophobic, π-π and hydrogen bonding interactions between them. The adsorption mechanism for target CMPs was verified by characterization techniques and molecular dynamics simulation. A method of POF-c coated stir bar sorptive extraction-high performance liquid chromatography-variable wavelength ultraviolet detector was developed for the analysis of four CMPs in corn and potato samples. Under the optimal conditions, LODs of the method were between 0.017 and 0.048 μg/L, and the linear range for four CMPs was 0.1/0.2-200 μg/L.

In this work, porous aromatic frameworks (PAFs) with different pore size were evaluated for simultaneous adsorption of 16 polycyclic aromatic hydrocarbons (PAHs) with large difference in polarity and molecular size. Two other porous organic polymers containing electron pushing/withdrawing group were investigated along for a comparison, and PAF-120 with the pore size of appr. 2.1 nm exhibited the highest extraction efficiency. Based on water contact angle and molecular dynamics simulation, the adsorption of 16 PAHs on PAF-120 was attributed to hydrophobic interaction, π-π interaction and molecular sieving effect. PAF-120/PDMS coated stir bar was then prepared by physical adhesion, and a method of stir bar sorptive extraction-gas chromatography-flame ionization detector was established for trace PAHs analysis in environmental samples. Under the optimal experimental conditions, the limits of detection (S/N = 3) for 16 PAHs were found to be in the range of 42-375 ng/L, with the relative standard deviations of 4.1-14.6% (n = 7). The enrichment factors varied from 31 (Indeno[1,2,3-cd]pyrene) to 80-fold (anthracene), with the maximal enrichment factor of 100-fold. The proposed method was applied to the analysis of PAHs in local environmental water and atmospheric particle samples. None of the 16 PAHs were detected in the collected water samples. While for the collected atmospheric particles, 12 PAHs were detected in fine particulate matter (PM

Magnetic composites of Fe

By monomer-mediated in-situ growth synthesis strategy, with hydroquinone and 1,3,5-tris(4-aminophenyl)benzene as monomers, a core-shell magnetic porous organic polymer was synthesized through a simple azo reaction. Based on this, a magnetic solid-phase extraction-high-performance liquid chromatography-fluorescence detection method was proposed for the analysis of fluoroquinolones in a honey sample. With ofloxacin, ciprofloxacin, enrofloxacin, lomefloxacin, and difloxacin as target analytes, factors affecting the extraction efficiency had been optimized. The LODs were 1.5-5.4 ng/L (corresponding to 0.23-0.81 μg/kg in honey). The linear range was 0.005-20 μg/L for difloxacin, 0.01-20 μg/L for ofloxacin, ciprofloxacin and lomefloxacin, and 0.02-20 μg/L for enrofloxacin. The enrichment factor was 84.4-91.7-fold with a high extraction efficiency of 84.4-91.7%. The method was assessed by the analysis of target fluoroquinolones in honey samples, and the recoveries for the spiked samples were 79.3-95.8%. The results indicated that the established magnetic solid-phase extraction-high-performance liquid chromatography-fluorescence detection method is efficient for the analysis of trace fluoroquinolones in honey.

Schiff base networks (SNWs) were introduced as a new stir bar coating, and a method of SNWs- coated stir bar sorptive extraction (SBSE) coupled to high performance liquid chromatography-ultraviolet detector (HPLC-UV) was developed for determination of pyrethroid pesticide residues in tobacco. The prepared amorphous SNWs polymer from melamine and 3,5-dihydroxybenzaldehyde riches in triazine rings, hydroxyl groups and amino groups, and the SNWs/polydimethylsiloxane (PDMS) stir bar prepared by sol-gel method can extract weakly polar pyrethroid pesticides through hydrophobic, π-π and hydrogen bonding. The SNWs/PDMS stir bar exhibited high extraction efficiency toward pyrethroid pesticides (70-76%) and good mechanical stability with reused time more than 50 times. Under the optimal experimental conditions, the limits of detection were 0.20 - 0.66 µg/L with relative standard deviation varying in the range of 2.3-8.2%, which meets the requirements of trace analysis of pesticide residues in the tobacco industry. The method was applied to the determination of six pyrethroid pesticides in cigarette samples, and the recovery for the spiked samples ranged from 82 to 117%, showing a great applicability for the analysis of pesticide residues in real samples with a complex sample matrix.

Herein, magnetic porous organic polymers (MOPs) prepared via an azo coupling reaction in water under mild conditions are evaluated for the extraction of seven cardiovascular drugs, including xylocaine, metoprolol, mexiletine, labetalol, propranolol, carvedilol and propafenone, from human urine samples for the first time. The extraction mechanisms are assumed to be electrostatic interaction and π–π stacking. The MOPs exhibited fast adsorption/desorption time (13 min) and high enrichment factors (315–365-fold) for target analytes. Based on this, a method coupling magnetic solid phase extraction with HPLC-UV detection was developed for the analysis of cardiovascular drugs. Under the optimized conditions, the LODs (S/N = 3) were in the range of 0.06–0.57 μg L−1 with an RSD (n = 5) of 4.3–8.6%, and the linear range was 0.2–200 μg L−1 for propranolol, 2–200 μg L−1 for metoprolol, and 0.5–200 μg L−1 for the other five analytes. The developed method was applied for the analysis of cardiovascular drugs in urine samples with recoveries of 89.0–112%. In order to further evaluate the application potential of this method, real-time monitoring of metoprolol in urine samples collected from volunteers treated with metoprolol tablets was performed. The proposed method is simple, fast, and sensitive and has good potential in the monitoring of cardiovascular drugs in competitive sports and clinical analysis.

Information on the risk of exposure to cerium oxide (CeO2) nanoparticles (NPs) is limited. To assess risk, we must know where and how such NPs are distributed to the body after exposure, both short- and long-term. In this work, an integrated approach of quantitative LA-ICP-MS bioimaging and fractionation was employed to study the translocation and transformation of CeO2 and Ce3+ in mouse spleen and liver. The complementary information retrieved by the two techniques above on the accumulation of Ce and dissolution/aggregation were found consistent. In brief, a detailed fine scanning of a region of interest in the organ was performed after fast-screening at low spatial resolution. In the spleen, after short-term high-dose exposure, CeO2 NPs was found mainly in the marginal zone and caused an up-regulation of Zn in the white pulp. After long-term low-dose exposure, CeO2 was found in the marginal zone and white pulp. In the liver, CeO2 NPs were mainly distributed in the Kupffer cells and lobule periphery. The high spatial resolution LA maps of HE this enabled an estimation of Ce content in Kupffer cells. Furthermore, fractionation by ultrafiltration was also employed to differentiate the ionic and NP species in the organs. This fractionation showed aggregation of Ce ions in spleen, supporting the LA-ICP-MS results. Transmission electron microscopy revealed that long-term CeO2 exposure triggered an immune response to infection in the spleen and confirmed the differential deposition of Ce in the marginal zone. The integrated analyses based on ICP-MS together with histology and TEM investigation suggests that long-term low doses of CeO2 NPs may cause toxicity in the liver and impair functions of the immune system.

Magnetic porous organic polymers (MOPs) were synthesized by a simple azo reaction, with 1,3,5-tris (4-aminophenoxy) benzene and 1,3,5-trihydroxybenzene as the monomers, and Fe3O4@SiO2 as the core. The preparation process was mild, green and environmental-friendly, avoiding the use of high temperature, metal catalysis and harmful organic reagent. The obtained MOPs were characterized in terms of morphology, pore structure, and magnetism; they exhibited high surface area, good stability/dispersibility, and excellent extraction performance for interest triazole fungicides (TFs). With the prepared MOPs as adsorbent, a method of magnetic solid phase extraction-gas chromatography-flame ionization detection (MSPE-GC-FID) was proposed for the analysis of target TFs in vegetables. After the vegetable samples were chopped and homogenized, acetonitrile was added for ultrasonic extraction, and the extract was diluted for subsequent MSPE process. Different operating conditions affecting the extraction efficiency of TFs, such as extraction time, pH, ionic strength, adsorbent dosage, and volume of sample as well as eluent were carefully optimized. Under the optimized experimental conditions, quantitative extraction could be achieved for target TFs (extraction efficiency of 84.5–90.3%), and the limits of detection were in the rage of 0.12–0.19 μg/L, which is the lowest among the reported GC-FID methods for target TFs presently. The linear range of the method for five TFs was 0.5–200 μg/L with the reproducibility of 2.6–6.8% (n = 7, c = 2 μg/L). The method was assessed by the analysis of target TFs in vegetables, and the recoveries for the spiked cucumber and cabbage were 86.9–117% and 84.7–114% (spiking levels of 80, 400 and 800 μg/kg), respectively, indicating that the matrix effect was negligible in the proposed MSPE procedure. The results show that the developed method of MSPE-GC-FID with MOPs as adsorbent is efficient for the analysis of trace TFs in vegetables.

Cellular uptake of Au NPs is the premise for their application in drug delivery, cell/tissue imaging and quantitation analysis of biomarkers in the cells. However, conventional methods for cell analysis may lead to the loss of important information from abnormal or atypical cells in the cell population. In this work, with 15, 30 and 60 nm Au NPs@citric acid and Au NPs@DNA as model materials, the cellular uptake of Au NPs in single HeLa cells is studied by using an on-line droplet chip inductively coupled plasma mass spectrometry hyphenated technique. It is found that the average amount of Au uptake for Au NPs@citric acid is higher than that for Au NPs@DNA at high incubation concentrations. The distribution of the number of uptaken Au NPs in single HeLa cells shows a great difference when HeLa cells are incubated with different Au NPs. The percentage of cells uptaking Au NPs in the cell population also reveals a difference in cellular uptake between Au NPs@citric acid and Au NPs@DNA at the single-cell level. To explain the abovementioned phenomenon, the endocytosis mechanisms of Au NPs are investigated. Clathrin-mediated endocytosis is found to be the major internalization pathway for 15 and 30 nm Au NPs@DNA.

Therapeutic drug monitoring is central to optimize therapeutic efficacy and minimize adverse events; however, the pharmacokinetics and pharmacodynamics of most drugs differ greatly among individuals. Evaluation of the therapeutic response is in urgent need to help clinician predict the clinical dose of drug. Herein, we described an analytical assay using gold nanocluster (AuNC)-decorated metal-organic frameworks (MOFs) for targeted drug delivery and monitoring pharmacodynamics, giving attractive options for studying individualized therapy. The camptothecin (Cam) anticancer drug was caged in the NH

Increasing use of TiO2 nanoparticles (NPs) leads to an accumulation in environment and a risk to human. In this work, an on-line monolithic capillary microextraction (CME)-inductively coupled plasma mass spectrometry (ICP-MS) method was developed for sensitive determination of TiO2 NPs in environmental water samples. With the presence of citric acid, TiO2 NPs can be selectively adsorbed on the poly(acrylamide)-vinylpyridine-methylene bis-(acrylamide) (poly(AA-VP-Bis)) monolithic column at pH 1, whereas Ti ions cannot be adsorbed. Factors affecting the extraction efficiency such as sample pH, concentration of citric acid and elution conditions were carefully investigated. Under the optimum conditions, a detection limit of 0.63 μg L−1 for TiO2 NPs and a sample throughput of 6 h−1 were achieved. The method can be applied to the determination of TiO2 NPs in the size range of 5–100 nm. The developed method was then applied to the analysis of TiO2 NPs in the East Lake water and Yangtze River water, and recoveries of 84–109% were obtained for spiked samples. Compared with other reported methods for the determination of metal oxide NPs, the developed on-line monolithic CME-ICP-MS has the merits of simple operation, high throughput and no need for digestion before ICP-MS detection.

For a deep understanding of arsenic's mutagenicity, carcinogenicity and teratogenicity, the elucidation of arsenic binding proteins in organisms is a necessary prerequisite. Herein, a biotinylated phenylarsenite (Bio-PAO(III)) probe was synthesized for in situ binding to arsenic binding proteins in HepG2 cells. The Bio-PAO(III)-arsenic binding proteins complexes were captured by the prepared streptavidin-magnetic beads (SA-MBs) by specific interaction of biotin-SA. After magnetic separation, the arsenic binding proteins in the eluent was separated by sodium dodecyl sulfate-polyacrylamide - gel electrophoresis, and the in-gel tryptic digested protein bands were subjected to capillary high performance liquid chromatography coupled with electrospray ionization mass spectrometry analysis. 32 kinds of arsenic binding proteins were identified in HepG2 cells, which could be divided into three groups, structure proteins, enzymes related with tricarboxylic acid cycle and fatty synthesis and transcriptional regulator. Poly [ADP-ribose] polymerase 1 and general transcription factor IIH subunit 1 were identified to bind with arsenicals, which may affect the process of nucleotide excision repair in HepG2 cells.

Time-resolved (TRA)-ICPMS has become a booming subfield of single-cell analysis tools in recent years, while generation of single cells remains the major challenge. Microfluidic devices reveal their great capability and potential in encapsulation of single cells into water droplets. However, current strategies to pinch off droplets require a specific oil phase, which is not compatible to conventional ICPMS and makes the signal of cells in the water phase susceptible. Herein, we built a 3D water-in-gas microfluidic device (3D W/G MFD) with commercially available components, producing single cell droplet enclosed by argon gas. By simply tuning the flow rate of gas and water, the droplets were generated to encapsulate single cells, which significantly reduced the probability of the single signal coming from multiple cells by 1 or 2 orders of magnitude compared to direct injection. The developed oil-free 3D W/G MFD was more friendly to online coupling with TRA-ICPMS than water-in-oil devices. The effect of Cd2+ on HepG2 cells was studied by single cell detecting total Zn with 3D W/G MFD-TRA-ICPMS, and the variation of labile Zn was explored by flow cytometry with an N-(6-methoxy-8-quinolyl)-p-toluenesulfonamide probe. To the best of our knowledge, this work pioneered the exploration of variation in cellular metal content and speciation at the single-cell level, compensating for the deficiency of speciation analysis based on TRA-ICPMS and providing new insights into exploring the complexity of biology.

Recent progress of stir bar sorptive extraction (SBSE) in the past six years is reviewed. The preparation methods including electrodeposition, self-assembly, solvent exchange, physical magnetic adsorption and electrostatic spinning, for the coated stir bar are summarized and compared, specifically for a specific material for coatings fabrication, e.g., carbon-based materials and metal organic frameworks. The emerging materials (e.g., graphene, graphene oxide, carbon nanotubes, monolith, metal-organic frameworks and porous organic polymers) applied for coated stir bar fabrication are one of the focus of this review, along with their respective advantages in extraction process and application in trace analysis. The development and application of extraction apparatus of SBSE are also involved. Based on these information, the development status and prospects of SBSE as an efficient sample pretreatment technique in real sample analysis are discussed.

Inductively coupled plasma mass spectrometry (ICP-MS) combined with element tags has been well designed and extensively applied in cell enumeration. It possesses superior quantitative capability, strong resistance to matrix interference, multiplex detection capability but destructive characteristic. Herein, we constructed an ICP-MS based multifunctional platform for capture, nondestructive enumeration, and release of circulating tumor cells (CTCs). Aptamer on capture probe recognized Mucin 1 (MUC1) on membrane of MCF-7 cells specifically, thus the cells were captured by probe and the Initiator originally hybridized with Aptamer was substituted by MUC1 and released into solution. Then the released Initiator was separated from the captured cells and hybridized with Tb labeled Substrate on detection probe to release a large amount of nicked Tb fragments through the nicking endonuclease assisted amplification for subsequent ICP-MS detection. Meanwhile, cells captured by probe were released by nuclease digestion for further reculture. Such a strategy effectively avoids CTCs destruction resulted from ICP-MS enumeration, increases the detection sensitivity of ICP-MS by involving nicking endonuclease assisted amplification, and realizes cell recovery for further analysis. A limit of detection of 87 MCF-7 cells and a linear range of 250-10 000 MCF-7 cells were realized for ICP-MS enumeration. A cell recovery of 52.7% (with capture and release efficiency of 63.9 and 82.5%, respectively) and a viability of 74.3% were obtained, meanwhile the released cells exhibited strong proliferation ability. This multifunctional platform for CTCs capture, enumeration, and release has great applicable potential in early diagnosis and individual treatment for cancer.

Ti (IV) modified vinyl phosphate magnetic nanoparticles (Fe3 O4 @SiO2 @KH570-PO4 -Ti (IV)) was prepared for simultaneous extraction of multiple arsenic species, followed by high performance liquid chromatography (HPLC) - inductively coupled plasma mass spectrometry (ICP-MS) analysis. Inorganic arsenic (iAs), dimethyl arsenic acid (DMA), monomethyl arsenic acid (MMA), p-amino phenyl arsenic acid (p-ASA), 4-hdroxyphenylarsenic acid (4-OH), phenyl arsenic acid (PAA) and 3-nitro-4-hydroxyphenylarsenic acid (ROX) were investigated as interest analytes. It was found that they were quantitatively adsorbed on Fe3 O4 @SiO2 @KH570-PO4 -Ti (IV) at pH 5, and desorbed completely with 0.1 mol/L sodium hydroxide solution. Enrichment factor of 100-fold was obtained by consuming 100 mL sample solution. Under the optimal conditions, the method combining MSPE with HPLC-ICP-MS presented a linear range of 1-5000 ng/L for seven arsenic species. The limits of detection were 0.39, 0.60, 0.23, 1.85, 0.54, 0.48 and 0.84 ng/L for DMA, MMA, p-ASA, iAs, 4-OH, PAA, ROX, with the relative standard deviations (c = 10 ng/L, n = 7) of 3.6, 3.9, 5.5, 12.4, 6.1, 5.8, 5.0, respectively. The accuracy of the method was validated by analyzing BCR 627 Tuna fish. The application potential of the method was further evaluated by chicken muscle and liver samples. No target arsenic species were detected in these samples, and good recoveries (80.6-123%) were obtained for the spiked samples at low, medium and high concentration levels. This article is protected by copyright. All rights reserved.

In this work, magnetic nanoporous carbons (MNPCs) based on Zn/Co-MOFs was synthesized via a facial one-step carbonization method. The prepared MNPCs exhibited high specific surface areas, good chemical stability and high extraction efficiency for interest organophosphorus pesticides (OPPs). The good extraction performance of the MNPCs for interest OPPs can be primarily attributed to π-π interaction and hydrophobic interaction between MNPCs and OPPs. Based on it, MNPCs-based MSPE-GC-FPD method was established for the quantification of five OPPs in fruit samples. The main experimental conditions for MSPE of five target OPPs were investigated systematically and optimized, such as the desorption solvent and volume, extracted volume, ionic strength, extraction time and desorption time. Under the optimal conditions, the limits of detection (LODs, S/N = 3) were found to be in the range of 0.018 (ethion) -0.045 (malathion) μg/L. The linearity was 0.05-100 μg/L for phorate, diazinon, ethion and 0.1-100 μg/L for malathion, fenthion respectively. The reproducibility of the method was in the range of 3.5-9.7%. The recovery experiments were carried out by spiking target OPPs at three concentration levels to validate the accuracy of the proposed method, and the recoveries for target OPPs were 84-116%. The results show that the proposed method in this work can be successfully used to analyze OPPs residue in fruit sample.

In order to comprehensively reflect the cigarette quality, a method combining direct injection of diluted sample with high sensitive high-performance liquid chromatography (HPLC)- electrospray (ESI)- quadrupole (Q)- time of flight (TOF)- tandem mass spectrometry (MS/MS) was developed for the identification of major components of cigarette essences (jujube and mulberry extracts). Based on the observed relative molecular mass, MS/MS fragmentation behavior, MS/MS database and related literatures, the components of the jujube extract and mulberry extract were identified. The result shows that the composition of jujube extract and mulberry extract has some similarity. They all mainly contain amino acids, free amino compounds and Maillard reaction products, which are the main constituents of a cigarette essence.

The content, migration and transformation of trace elements in living organisms play an important role in physiological activities. The analysis of trace elements in cells is of great significance to understand the function mechanism of trace elements in cells and organisms. Compared with conventional bulk analysis, many medical and clinical researches benefit from cell heterogeneity via single-cell analysis. Time-resolved analysis-inductively coupled plasma-mass spectrometry (TRA-ICP-MS) based strategies have the potential for both counting and quantitative assessment. It has been used to evaluate cell-to-cell difference in elemental content, cellular uptake of metal-containing drugs and nanoparticles. This review focuses on TRA-ICP-MS based methodologies for single-cell analysis over the past few decades. Recent advances in ICP-MS instrumentations (cell introduction systems and mass spectrometers), microfluidic platforms and their in-depth applications in single-cell analysis are summarized. This review also prospects future developments of TRA-ICP-MS for single-cell analysis.

Arsenite (As(III)) has been considered as a human carcinogen associated with many human cancers especially skin cancer. Elucidation of the transformed species of As(III) during its metabolism in cells is beneficial for evaluation of its bioeffect. In this work, a hyphenated method of reversed phase ion pair high performance liquid chromatography - inductively coupled plasma mass spectrometry (RP-IP-HPLC-ICP-MS) equipped with collision/reaction cell technology (CCT) was developed for speciation of As(III) and its metabolites (arsenate [As(V)], monomethylarsonic acid [MMA(V)], and dimethylarsinic acid [DMA(V)]) in SCC-7 cells. The developed analytical method exhibits low limits of detection for interest arsenic species in the range of 14-27 ng/L and wide linear range up to four orders of magnitude, providing a sensitive tool for arsenic metabolites analysis and further understanding the metabolism of As(III) in SCC-7 cells. The effect of exposure time, exposure concentrations and elimination time on the arsenic species and total arsenic in SCC-7 cells incubated by As(III) were systematically studied. At low exposure concentrations (5 μM), large proportion of intracellular As(III) transformed to methylated metabolites, and the final methylated metabolite DMA(V), which could not be completely removed from the cells in the elimination process, is considered to play as the primary carcinogen. While at high exposure concentrations (5 μM), most of intracellular As(III) probably bound to biomacromolecules rather than followed biomethylation process, exhibiting different metabolism.

In this work, ethylenediamine modified poly(glycidyl methacrylate-ethylene dimethacrylate)(poly(GMA-EDMA-NH2)) was prepared for highly selective extraction of Se(VI) with high adsorption capacity of 0.825 mg m−1 (530 µm i.d.). Based on it, a novel method of polymer monolithic capillary microextraction (CME) on-line coupling with inductively coupled plasma-mass spectrometry (ICP-MS) was developed for the determination of inorganic selenium species (Se(IV)/Se(VI)) in natural waters. Under the optimized conditions, the analytical performance of the proposed on-line CME-ICP-MS method was evaluated for Se(VI). The limit of detection for Se(VI) was 14.2 ng L−1, and the enrichment factor was 50-fold with the sample throughput of 5 h−1. For Se(IV), the concentration was obtained by subtracting Se(VI) from the total Se(VI) obtained by the proposed method after oxidation of Se(IV) to Se(VI). The accuracy of the method was validated by the analysis of a Certified Reference Materials of GBW(E)080395. The proposed method was applied for the analysis of inorganic selenium species in natural waters with good recoveries. The developed method of monolithic CME-ICP-MS is sensitive, simple and rapid for the analysis of inorganic selenium species in natural waters.

A melamine-based porous organic polymer (mPMF) was synthesized as solid phase extraction (SPE) adsorbent for inline SPE-high performance liquid chromatography (HPLC)-ultraviolet detector (UV) analysis of five phytohormones. Melamine contributed to the rich π-electron and N-containing triazine structure for mPMF, which could form π-π interaction and intermolecular hydrogen bond with COOH containing phytohormones. The synthesized mPMF adsorbent shows extremely high extraction efficiency for five target analytes (>80%) including salicylic acid, indole-3-acetic acid, abscisic acid, 2,4-dichlorophenoxyacetic acid and 1-naphthalene acetic acid. The factors affecting extraction of the target phytohormones were investigated and the optimized experimental conditions were established. The linear range was 0.2–100 μg/L with the limits of detection in the range of 0.06–0.11 μg/L for five target phytohormones. The developed method of mPMF-inline-SPE-HPLC-UV was applied for the analysis of trace target phytohormones in tomato and grape juice samples, and the recovery in the range of 83.1–116% and 87.2–121% was obtained for the spiked tomato and grape juice, respectively. This method has the advantages of high sensitivity and good reproducibility, and it has good application potential for the analysis of phytohormones in fruit samples. Moreover, inline analysis avoided the problems of sample pollution and sample loss, and provided a sample throughput of 5/h.

In this work, poly(1-vinylimidazole-ethyleneglycol dimethacrylate) (poly(VI-EDMA)) monolith coated stir bars were synthesized by one-pot polymerization, and they exhibited higher extraction efficiency and faster extraction dynamics for selected PFAAs than commercial ethylene glycol modified silicone (EG-silicone) and polydimethylsiloxane (PDMS) coated stir bars. Taking eleven PFAAs as target analytes, including C4-C12 perfluoroalkyl carboxylates (PFCAs) and C6, C8 perfluoroalkane sulfonates (PFSAs), a method combining monolith-based stir bar sorptive extraction (SBSE) with high performance liquid chromatography (HPLC) − electrospray tandem mass spectrometry (ESI–MS/MS) was proposed for the determination of multiplex PFAAs in environmental water samples. Under the optimized conditions, low limits of detection (0.06–0.40 ng/L) and wide linear range (0.6–400 ng/L) were obtained for target PFAAs with. The developed method was then applied for the analysis of target PFAAs in environmental water samples, and recoveries of 80.1–117% and 80.3–122% were obtained for target PFAAs in spiked Yangtze River and East Lake water samples respectively.

A switchable hydrophilicity solvent (SHS) based liquid phase microextraction (LPME) method was proposed for the preconcentration of trace Pb (II) and Cd (II) followed by graphite furnace atomic absorption spectrometry (GFAAS) detection. The SHS of protonated triethylamine carbonate (P-TEA-C) was synthesized and applied as the extractant, which is environmentally friendly and low cost. Pb (II) and Cd (II) in ammonium pyrrolidine dithiocarbamate (APDC) complex form was extracted into the triethylamine (TEA) phase by converting P-TEA-C to TEA. The vortex led to the rapid formation of fine droplets of the extractant in the aqueous solution, and enlarged contact surface between both immiscible liquids. The factors affecting the microextraction procedure, including sample pH, APDC concentration, volume of SHS and NaOH, sample volume and matrix effect were investigated. Under the optimal conditions, enrichment factor of 50 was achieved with consumption of 10 mL aqueous sample, and detection limits of 16 and 3.9 ng L−1 were obtained for Pb (II) and Cd (II), respectively. The accuracy of the proposed method was validated by the analysis of Certified Reference Materials of GSBZ50009-88 environmental water, GBW07605 tea and GBW07601(GSH-1) human hair. The method was also successfully applied for determination of Pb (II) and Cd (II) in water, tea and human hair samples.

A method based on ion-pair reversed phase high performance liquid chromatography (HPLC) hyphenated with inductively coupled plasma mass spectrometry (ICP-MS) was developed for arsenic speciation in extract of tree moss. Under the optimal conditions, the limit of detection of eight arsenic species including arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA), dimethylarsonic acid (DMA), trimethylarsinoxide (TMAO), tetramethylarsonium (Tetra), arsenocholine (AsC) and arsenobetaine (AsB) is between 0.04 and 0.07 ng/mL, with a linear range of 0.2 - 500 ng/mL. Three unknown arsenic species (Unk1, Unk2 and Unk3) and six specific arsenic species (AsIII, AsV, DMA, TMAO, Tetra and AsB) were detected in the extract of tree moss. Unk3 was identified as a kind of arsenosugars (2,3-dihydroxypropyl-5-deoxy-5(dimethylarsenoso)furanoside, arsenosugar X) by electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-qTOF-MS).

In this study, poly(1-vinylimidazole) functionalized gold ion imprinted polymer coated magnetic nanoparticles (MNPs@PVIM-Au-IIP) were prepared and characterized. The adsorption behaviors of the prepared MNPs@PVIM-Au-IIP toward gold ions (Au(III)) were studied, it was found that MNPs@PVIM-Au-IIP has good selectivity, high adsorption capacity (185.4 mg g−1) and fast adsorption kinetic for Au(III). Based on it, a new method of ion imprinted magnetic solid phase extraction (II-MSPE) coupled with graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the analysis of trace Au(III) in real samples with complicated matrix. Factors affecting MSPE including sample pH, desorption reagent, elution concentration and volume, elution time, sample volume and adsorption time were optimized. With high enrichment factor of 100-fold, the detection limit of the proposed method is 7.9 ng L−1 for Au(III) with the relative standard deviation of 7.4% (c = 50 ng L−1, n = 7). In order to validate the accuracy of the proposed method, the Certified Reference Material of GBW07293 geological sample (platinpalladium ore) was analyzed, and the determined value was in good agreement with the certified value. The proposed II-MSPE-GFAAS method is simple, fast, selective, sensitive and has been successfully applied in the determination of trace Au in ore, sediment, environmental water and human urine samples with satisfactory results.

In this study, spherical imine-linked covalent organic frameworks (COFs) were fabricated from 2,5-dimethoxybenzene-1,4-dialdehyde (DMTP) and 1,3,5-tris (4-aminophenyl) benzene (TAPB) and named as TAPB-DMTP-COFs. The resulting powders were coated onto bare glass bars via physical-adhesion to obtain TAPB-DMTP-COFs coated stir bars. The self-made stir bars exhibited higher extraction efficiency (74–85%) and faster dynamics (50 min) towards non-steroidal anti-inflammatory drugs (NSAIDs) over ethylene glycol-Silicone (42–68%, 180 min) and polydimethylsiloxane (3–61%, 180 min) coated stir bars. Fourier transform infrared (FT-IR) spectra, X-ray photoelectron spectroscopy (XPS), zeta potential and water contact angle were employed to provide a comprehensive understanding of the adsorption mechanism between the coating and analytes. The results displayed that methoxy group worked as an adsorption site helping the adsorption of interest NSAIDs onto the TAPB-DMTP-COFs coating and hydrogen bonds formed between the O atoms and the analytes. Additionally, the adsorption mechanisms possibly also involved π-π interaction and hydrophobic interaction. Moreover, TAPB-DMTP-COFs coated stir bars exhibited good stability and could be reused more than 60 times. Subsequently, a method by combining TAPB-DMTP-COFs coated stir bar sorptive extraction (SBSE) with liquid chromatography (HPLC)-ultraviolet detector (UV) was established for the determination of four NSAIDs in environmental waters. Under the optimized conditions, the established method showed a wide linear range of 0.2/1–500 μg/L for interest NSAIDs, the limits of detection varied from 0.039 to 0.312 μg/L. Yangtze River water, East Lake water and Spring water were subjected to the proposed method, the recoveries in spiked samples were 84.7–104%, 81.2–101% and 82.6–97.6%, respectively.

Cyanuric chloride and 4,4′-diamino-p-terphenyl were adopted as monomers to synthesize poly (4,4′-diamino-p-terphenyl-triazine) (PDT) covalent organic polymer. PDT coated stir bar was prepared and evaluated for the extraction of five phthalate esters (PAEs) with relatively lower logP values (2.7-4.9), including diethyl phthalate, diallyl phthalate, dipropyl phthalate, benzylbutyl phthalate and dibutyl phthalate. It exhibited higher extraction recovery (> 65%) and faster extraction kinetics (50 min vs 240 min) for target PAEs over commercial polydimethylsiloxane coated stir bar. Based on the superior performance, PDT coated stir bar sorptive extraction was combined with high-performance liquid chromatography-diode array detection for trace analysis of five PAEs plasticizers. The limits of detection for target PAEs were 0.04-0.27 μg/L, with the enrichment factors of 54-80-fold. The potential of the method was demonstrated by detecting five target PAEs in Chinese liquor and mineral water samples. No target analytes were detected in Chinese liquor sample, and recoveries of 85.4-109% were obtained for target analytes in spiked liquor samples; trace diethyl phthalate (1.19-2.98 μg/L) and dibutyl phthalate (0.77-0.91 μg/L) were detected in two mineral water samples, with recoveries of 85.4-117% and 87.4-117% respectively in spiked mineral water samples.

Development of multimodal detection technologies for accurate diagnosis of cancer at early stages is in great demand. In this work, we report a novel approach using an aptamer-based dual-functional probe for rapid, sensitive, and specific counting and visualization of MCF-7 cells by inductively coupled plasma–mass spectrometry (ICP-MS) and fluorescence imaging. The probe consists of a recognition unit of aptamer to catch cancer cells specifically, a fluorescent dye (FAM) moiety for fluorescence resonance energy transfer (FRET)-based “off-on” fluorescence imaging as well as gold nanoparticles (Au NPs) tag for both ICP-MS quantification and fluorescence quenching. Due to the signal amplification effect and low spectral interference of Au NPs in ICP-MS, an excellent linearity and sensitivity were achieved. Accordingly, a limit of detection of 81 MCF-7 cells and a relative standard deviation of 5.6% (800 cells, n = 7) were obtained. The dynamic linear range was 2 × 102 to 1.2 × 104 cells, and the recoveries i...

A novel magnetic N-doped porous carbon material (MNPC) was obtained by mixing urea, sucrose and Fe3O4@SiO2 and calcinating for carbonization. With g-C3N4 as intermediate template, the synthesized material has large BET surface area of 219.4 m2 g−1 and high nitrogen content of 9.4 wt%. With using MNPC material as sorbent, a new method by coupling magnetic solid phase extraction (MSPE) with inductively coupled plasma mass spectrometry (ICP-MS) was established for enrichment and determination of Cd(II) and Pb(II) in environmental waters. The conditions affecting MSPE were optimized including the effects of pH, sample volume, amount of sorbent usage, adsorption/desorption time and eluent type/concentration/volume. Under the optimized conditions, the developed MSPE-ICPMS method exhibited a good linear dynamic range of more than three orders of magnitude (2–5000 pg mL−1 for Cd(II) and 10–5000 pg mL−1 for Pb(II)) and a low detection limits of 0.49 and 3.1 pg mL−1 for Cd(II) and Pb(II), respectively. The relative standard deviations were in the range of 6.9%–7.3% for the target metal ions. The adsorption/desorption kinetics of the developed MSPE procedure was fast, and the total extraction procedure only cost 7 min (5 min for adsorption and 2 min for desorption) for each sample. The sorbent could be used for at least 5 times. The MSPE-ICPMS method has great potential for the determination of trace and even ultra-trace Cd(II) and Pb(II) in the environment waters.

In recent years, single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) has become a powerful tool for biological quantitative analysis. Homogeneous analysis method requires no separation and washing steps, which is suited for the analysis of highly infectious pathogens, so as to reduce the risk of infection during the operation. SARS-CoV-2 spreads all over the world, and its early infection symptoms are similar to influenza, which brings inconvenience to triage. Therefore, developing novel analytical method for simultaneous detection of multiple viral nucleic acids is essential. Taking the advantages of SP-ICP-MS and homogeneous analysis strategy, a SP-ICP-MS homogeneous nucleic acid assay by using gold nanoparticles (Au NPs) and silver nanoparticles (Ag NPs) probes was established for simultaneous sensitive analysis of SARS-CoV-2 and influenza A (H3N2). In the present of target SARS-CoV-2 or H3N2 nucleic acids, corresponding Au NPs or Ag NPs probes form larger aggregates, resulting in increased pulse signal intensity and reduced pulse signal frequency of the corresponding NPs in SP-ICP-MS measurement. In this assay, the reaction system of Au NPs and Ag NPs probes does not interfere with each other, and there was no separation and washing procedure, which facilitates operation, saves the analysis time, and improves the analysis efficiency. The linear range of this method is 5–1000 pmol L−1, with low-level limits of quantification of target nucleic acid. The developed SP-ICP-MS simultaneous homogeneous detection method has a good potential for detecting nucleic acid, protein, cell and other biological samples by changing different modification sequences on the NPs probes., Graphical abstract Image 1

A novel adsorbent of magnetic graphene oxide (GO) chemically modified by cysteamine hydrochloride (Fe3O4@SiO2/GO-NH2) through thiol-ene click chemistry reaction was synthesized. The prepared Fe3O4@SiO2/GO-NH2 exhibit selective adsorption to As(V) with high adsorption capacity (52.66 mg g−1). Taking Fe3O4@SiO2/GO-NH2 as the adsorbents, a new method of magnetic solid phase extraction (MSPE) combined with graphite furnace atomic absorption spectrometry (GFAAS) was developed in determining trace-level inorganic arsenic species (As(III) and As(V)) in environmental water and bottled water samples. Various experimental parameters affecting the MSPE have been optimized. Under the optimal experimental parameters, the limit of detection of the established method for As(V) was 1.02 ng L−1, the relative standard deviations were 7.9% (intra-day, c = 50 ng L−1, n = 5) and 4.6% (inter-day, c = 50 ng L−1, n = 7), respectively, and the enrichment factor of the method was 392. GBW08666 and GBW08667 (certified reference material) were analyzed to confirm the accuracy of the method, and the results were matched well with the certified values. The established MSPE-GFAAS method was successfully applied in analyzing trace/ultratrace As(III) and As(V) in real water samples.

This review focuses on magnetic nanomaterials as sorbents for trace elements analysis in environmental and biological samples. The design and preparation of magnetic nanomaterials with specific functional groups for trace elemental analysis are summarized, along with relevant adsorption mechanism. The application of these magnetic sorbents in different operation modes for the quantification of trace elements and their species in environmental and biological samples are discussed. The trend of development in this field is also prospected.

The use of porous carrier and coating sorbents in stir bar sorptive extraction (SBSE) contributes to the improvement of extraction efficiency and dynamics. Herein, porous nickel foam (NF) with large surface area and magnetic property was used as the carrier of stir bar. NF was added into the mixture of graphene oxide (GO) and reducing agent, and reduced graphene oxide (RGO) coating was obtained on the surface of NF substrate by in situ hydrothermal reduction. The characterization results of Fourier transform infrared spectroscopy, X-ray power-diffraction and scanning electron microscope showed that GO was partially reduced into RGO, and the RGO coating was uniformly loaded on the NF surface. The obtained RGO-NF composite was used as the stir bar coating for the analysis of six benzotriazole (BZTs) UV absorbents. The extraction efficiency was between 48 and 64% for six BZTs. RGO-NF stir bar exhibited faster adsorption/desorption kinetics than commercial polydimethylsiloxane coated stir bar (50 min vs 120/360 min) due to its porous structure and large specific surface area. On this basis, a method of RGO-NF coated stir bar sorptive extraction combined with high performance liquid chromatography (HPLC)-DAD was established for the determination of six BZTs. Under the optimized conditions, the limits of detection were 0.33–0.50 μg/L for six target BZTs, and the linear range was 1–100 μg/L. The proposed method merits good ability to resist matrix and was used to analyze six BZTs in environmental water samples. The recoveries of target BZTs were obtained within 83.0–112% in the spiked East Lake water and 97.0–111% in the spiked Yangtze River water, respectively.

Avian influenza viruses are the pathogens of global poultry epidemics, and may even cause the human infections. Here, we proposed a novel inductively coupled plasma mass spectrometry (ICP-MS) based immunoassay with gold nanoparticles (Au NPs) labeling for the determination of H9N2 virions. Magnetic-beads modified with anti-influenza A H9N2 hemagglutinin mono-antibody (mAb-HA) were utilized for the capture of H9N2 virions in complex matrix; and Au NPs conjugated with mAb-HA were employed for the specific labeling of H9N2 virions for subsequent ICP-MS detection. With a sandwich immunoassay strategy, this method exhibited a high specificity for H9N2 among other influenza A virions such as H1N1 and H3N2. Under the optimized conditions, this method could detect as low as 0.63 ng mL − 1 H9N2 virions with the linear range of 2–400 ng mL − 1 , the relative standard deviation for seven replicate detections of H9N2 virions was 7.2% (c = 10 ng mL − 1 ). The developed method was applied for the detection of H9N2 virions in real-world chicken dung samples, and the recovery for the spiking samples was 91.4–116.9%. This method is simple, rapid, sensitive, selective, reliable and has a good application potential for virions detection in real-world samples.