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ANALYTICA CHIMICA ACTA · 2023 · IF 6.2

Ultrasensitive determination of selenium in water and food samples by ICP-MS: UiO-66-NH2 for preconcentration and direct slurry hydride generation

Qing Yang,Chenghui Li,Jing Hu,Xiandeng Hou

Background Selenium is an indispensable microelement for humans and food is the main source of selenium intake. As one of the best techniques for the determination of selenium, inductive coupling plasma-mass spectrometry (ICP-MS) features some unique advantages, such as wide linear range and high sensitivity. Nevertheless, it still remains a challenge to achieve the accurate and high sensitivity determination of ultra-trace selenium in food samples by ICP-MS owning to the high first ionization energy of selenium and interferences from sample matrices as well as isobaric interferences. Results In this work, UiO-66-NH 2 (metal organic framework, MOF) was fast synthesized by microwave method and employed for the preconcentration of ultra-trace selenium with an adsorption efficiency of nearly 100 %. The selenium-adsorbed MOF was collected by filtration, and then simply converted to slurry for in situ hydride generation (HG) for sensitive detection of selenium by ICP-MS. Various factors affecting the adsorption of selenium by the MOF (including pH, adsorption time, and amount of MOF) together with main parameters of hydride generation (including concentrations of HCl and NaBH 4 ) were carefully evaluated. Experimental results show that effective matrix separation can greatly reduce interference, with an excellent detection limit of 1 ng/L. The practicability and accuracy of this method were successfully confirmed by the determination of trace selenium in several food samples. Significance UiO-66-NH 2 (MOF) was used as an effective adsorbent for the preconcentration of selenium prior to direct slurry sampling HG-ICP-MS determination. Direct slurry sampling avoided additional elution procedures and was conducive to eliminating matrix and isobaric interferences. High sensitivity and interference-free determination were achieved for determination of ultra-trace Se in complex food samples.

CAS / MDL: 10312-55-7
研究领域: 分析化学 · 环境科学 · 食品安全
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2025 · IF 1.6

A rapid method for determination of ultra-trace level Pu isotopes in atmospheric particulate matter samples using SF-ICP-MS and TEVA resin

Xin Futao,Luo Min,Li Chun,Ma Lingling,Xu Diandou,Xu Gang,Li Xi,Shao Yang

A rapid method has been developed for determining ultra-low level Pu isotopes in atmospheric particulate matter samples using SF-ICP-MS and TEVA resin. The Pu purification, ashing conditions and microwave digestion, were optimized to achieve high decontamination factor of U (4.1 × 10 4 ) and stably high Pu recovery (80–90%). The method detection limits were estimated to be 0.83 fg/g for 239 Pu and 0.70 fg/g for 240 Pu. Four IAEA certified reference materials were used for method evaluation. Finally, the method was successfully applied to determine the source of Pu in atmospheric particulate matter samples. The method can be performed within 16 h.

研究领域: 环境科学 · 核化学 · 分析化学
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NEW JOURNAL OF CHEMISTRY · 2019 ·Vol. 43 ·期 9 ·3946-3955 · IF 3.069

Single particle ICP-MS and GC-MS provide a new insight into the formation mechanisms during the green synthesis of AgNPs

Huiling Zhang,Yuxiong Huang,Jianqiang Gu,Arturo Keller,Yuwei Qin,Yue Bian,Kun Tang,Xiaolei Qu,Rong Ji,Lijuan Zhao

Green synthesis of metallic nanoparticles (NPs) using plant extracts has received considerable attention due to its environmentally and economically friendly nature. Various metabolites in plants such as amino acids, organic acids, sugars and phenolic compounds have been speculated to be responsible for the synthesis of metallic NPs in previous studies. However, to date, there has been a lack of direct evidence linking specific metabolites to the reduction of metal ions to form metallic NPs. Here, AgNPs are synthesized using cucumber leaf extract and characterized by UV-visible spectroscopy, dynamic light scattering (DLS) and transmission electron spectroscopy (TEM). Single particle inductively coupled plasma mass spectrometry (sp-ICP-MS) was used to investigate the size of newly synthesized NPs as well as the kinetics of particle formation. Gas chromatography–mass spectrometry (GC-MS) based metabolomics identified and quantified 245 metabolites in cucumber leaf extracts. By comparing the concentrations of metabolites before and after the reaction, the metabolites responsible for the synthesis were screened out. Reducing sugars (cellobiose, ribulose-5-phosphate, melibiose, 2-deoxy-D-glucose, tagatose, fructose, ribose, 3,6-anhydro-D-galactose) were markedly decreased after the reaction, indicating that reducing sugars are involved in the biosynthesis process and possibly function as reducing agents. The key thermodynamic data of the reaction between Ag+ and reducing sugars were obtained by using isothermal titration calorimetry (ITC), which further confirmed the interaction between Ag+ and metabolites. This study provides a deep insight into the reaction process and mechanism of green synthesized AgNPs.

CAS / MDL: 1336-21-6
研究领域: 环境科学 · 纳米生物学
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ANALYTICA CHIMICA ACTA · 2025 · IF 6

LA-ICP-MS-quantitated boronate affinity magnetic Zr-MOFs prepared via post-modification for glycopeptides enrichment

Feng Zhang,Sen Zhang,Xing Liu,Wei Gao,Jun Luo,Yi-fan Pan,Wei-Juan Zheng,Xin Hu,Hong-zhen Lian

Background Glycoproteins are critical in various biological processes and attract lots of attention of researchers. It still remains a challenge to detect glycopeptides by mass spectrometry because of their low abundance with heterogeneity and lability, as well as signal suppression by non-glycopeptides. The boronate affinity-based enrichment is an effective solution for detecting cis -diols-containing compounds including glycopeptides in complex matrices. However, there has not been any report about absolute quantitation of boron in the absorbent materials for glycopeptides, which obstructed the tailored design of boronate affinity materials and deeper understanding of interaction mechanisms. Results This work presents the development of a boronic acid-functionalized magnetic zirconium metal-organic framework (mMOF–AAPBA) with actual boron content for specific capture of glycopeptides. The synthesized nanocomposite could enrich glycopeptides by magnetic solid-phase extraction (MSPE) via the synergistic effect of hydrophilic interaction and boronate affinity. After full characterization including quantitative analysis of boron by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), mMOF–AAPBA was applied as MSPE absorbent to capture glycopeptides. Under the optimized conditions, it could enrich 28 glycopeptides both from horseradish peroxidase and immunoglobulin digests, with a limit of detection of 1 fmol μL −1 coupled with matrix-assisted laser desorption/ionization time of flight mass spectrometry. The boronate affinity absorbent also possessed great ability of anti-interference and good reusability. Furthermore, it possessed high performance in enriching glycopeptides in real samples including human saliva and traditional Chinese medicine injections. Significance In the preparation of the boron-containing nanocomposites, there is a special interest that an accurate protocol was established to assay boron based on LA-ICP-MS assisted by home-made matrix reference substances for the first time. These findings highlight the quantitative boron-containing mMOF–AAPBA as a robust affinity material for glycopeptide enrichment in real biological samples, offering potential applications in glycoproteomics and other cis -diols compound related researches.

研究领域: 分析化学 · 生物化学 · 纳米技术 · 质谱学 · 糖蛋白质组学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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CHROMATOGRAPHIA · 2018 ·Vol. 81 ·期 6 ·881-889 · IF 1.401

Determination of Metallothionein Isoforms in Fish by Cadmium Saturation Combined with Anion Exchange HPLC-ICP-MS

Li Shan,Yang Zhaoguang,Cao Junfei,Qiu Bo,Li Haipu

Abstract The content of metallothionein (MT) in fish can serve as a biomarker for heavy metal contamination in an aquatic environment. In this paper, an improved sample separation and quantification method using cadmium saturation combined with anion exchange high performance liquid chromatography–inductively coupled plasma mass spectrometry (HPLC–ICP-MS) was developed to measure the two major isoforms of MT (MT-I and MT-II) in fish. Replacing sulfur with cadmium as the quantitative element by cadmium saturation reduced the instrumental requirement and analysis cost. In the chromatographic separation, NH 3 –NH 4 Cl buffer was applied as the mobile phase instead of Tris–HCl buffer to prevent carbon deposition on the ICP cone. The chloride concentration was found to be a key factor to the separation of MT-I and MT-II, and the optimum chromatographic condition was 27 mM of NH 3 –NH 4 Cl in isocratic mode, with a pH of 8.6 and a flow rate of 0.8 mL min −1 . The limits of detection were 0.7 μg g −1 for MT-I and 1.0 μg g −1 for MT-II, with recoveries ranging from 96.2 to 104.2% for MT-I and 84.7 to 90.4% for MT-II in different fish tissues. The relative standard deviations were less than 8% for both isoforms. Graphical abstract

研究领域: 环境科学 · 分析化学 · 毒理学
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TALANTA · 2018 · IF 4.244

Simultaneous competitive and sandwich formats multiplexed immunoassays based on ICP-MS detection

Yuqing Zhang,Gongwei Sun,Yi Zhang,Biao Huang,Zhi Xing,Sichun Zhang,Xinrong Zhang

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) based immunoassay method has been proposed in multiple immunoassays but has not been used in competitive and sandwich formats immunoassay simultaneously. The two immunoassays were usually conducted separately in clinical field depending on the size and the amount of binding sites of targets. We proposed an immunoassay method based on magnetic beads and ICP-MS detection that could be suitable for both small and large molecules. The functionalized magnetic beads were added to capture the immune complex after immune reaction. In this way, thyrotropin and free thyroid hormone can be captured, separated and then detected according to the elemental tags by ICP-MS simultaneously. The new method was evaluated by comparing the results with time resolved fluorescence immunoassays (TRFIA). The dynamic ranges of TSH and FT 4 were 0.16–105 mU/L and 3.5–65 pmol/L, respectively. The limits of detections were 0.06 mU/L for TSH and 1.59 pmol/L for FT 4 . And the relative standard deviations (RSD) of TSH and FT 4 were 4.64% at 2.5 mU/L and 1.87% at 5.85 pmol/L. This immunoassay method enables the determination of small and large biomolecules simultaneously via competitive and sandwich immunoassay formats.

CAS / MDL: 13759-92-7
研究领域: 分析化学 · 临床化学 · 生物医学工程
✓ 已验证 产品关联 DOI PubMed 高影响因子
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TALANTA · 2024 · IF 5.6

In situ characterization of silver nanoparticles sulfidation processes in aquatic solution by hollow fiber flow-field flow fractionation coupled with ICP-QQQ

Qingsheng Bai,Qingcun Li,Zhiqiang Tan,Jingfu Liu

The sulfidation is considered as one of the most important environmental transformation processes of silver nanoparticles (AgNPs), which affects their transport, uptake and toxicity. Herein, based on the hollow fiber flow-field flow fractionation coupled with triple quadrupole inductively coupled plasma mass spectrometry (HF5-ICP-QQQ), we developed an efficient approach to accurately characterize the sulfidation process of AgNPs in aquatic solutions. HF5 could efficiently remove interferential ions and separate nanoparticles with different sizes online, and ICP-QQQ could accurately detect S element through monitoring 32 S 16 O + in mass shift mode. By the proposed method, two kinds of AgNPs, citrate-coated AgNPs and PVP-coated AgNPs, were selected as models to trace their transfer behaviors during the sulfidation. The results showed once AgNPs were exposed to Na 2 S solution, the overlapping fractograms of 32 S 16 O + and 107 Ag + were rapidly detected by HF5-ICP-QQQ to indicate the co-presence of Ag and S, and thus confirming the production of Ag 2 S and AgNPs underwent a rapid sulfidation process. There were substantial differences in the influence of the two coated agents on the stability of the particles under the conditions examined. In the presence of sulfide, PVP-coated AgNPs could maintain initial size distribution with higher stability, while the size distribution of citrate-coated AgNPs changed considerably. The developed HF5-ICP-QQQ method provides a reliable tool to identify and characterize the transformation process of AgNPs in aquatic solution, which contributed to a deeper understanding of the environmental fate and behavior of AgNPs with different coating.

研究领域: 环境科学 · 分析化学
✓ 已验证 DOI PubMed 高影响因子
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GEOSTANDARDS AND GEOANALYTICAL RESEARCH · 2024 · IF 2.7

Determination of Rare Earth Elements, Zirconium, Hafnium, Thorium and Uranium in Ultramafic Rocks by ICP-MS after RE-UTEVA Resin Columns for Separation and Pre-Concentration

Qiuyun Guan,Xudong Guo,Yali Sun,Xiaoming Liu,Shouqian Zhao

A simple method was developed for the determination of REEs, Zr, Hf, Th and U in ultramafic rocks by inductively coupled plasma-mass spectrometry with a combination of RE and UTEVA extraction resins for their separation and pre-concentration. Ultramafic rocks were digested with HNO 3 -HF-HClO 4 and finally turned into 11 mol l −1 HCl solutions together with H 3 BO 3 to remove insoluble fluorides. The removal of matrix elements was achieved during the loading procedure. Following this, REEs on RE resin, and Zr, Hf, Th and U on UTEVA resin were eluted with 10 ml of 0.24 mol l −1 HCl, with recoveries better than 94.4%. This method was validated using reference materials JP-1, DTS-2B, OKUM, UB-N, MUH-1 and DZΣ-2, and the measurement results for target analytes were comparable to literature values, indicating its applicability to the determination of REEs, Zr, Hf, Th and U at ultra-trace level in ultramafic rocks.

CAS / MDL: 10043-35-3 7601-90-3
研究领域: 地球化学 · 分析化学
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TALANTA · 2017 · IF 4.162

An environmentally-friendly, highly efficient, gas pressure-assisted sample introduction system for ICP-MS and its application to detection of cadmium and lead in human plasma

Yupin Cao,Biyang Deng,Lizhen Yan,Hongli Huang

An environmentally friendly and highly efficient gas pressure-assisted sample introduction system (GPASIS) was developed for inductively-coupled plasma mass spectrometry. A GPASIS consisting of a gas-pressure control device, a customized nebulizer, and a custom-made spray chamber was fabricated. The advantages of this GPASIS derive from its high nebulization efficiencies, small sample volume requirements, low memory effects , good precision, and zero waste emission. A GPASIS can continuously, and stably, nebulize 10% NaCl solution for more than an hour without clogging. Sensitivity, detection limits, precision, long-term stability, double charge and oxide ion levels, nebulization efficiencies, and matrix effects of the sample introduction system were evaluated. Experimental results indicated that the performance of this GPASIS, was equivalent to, or better than, those obtained by conventional sample introduction systems. This GPASIS was successfully used to determine Cd and Pb by ICP-MS in human plasma.

研究领域: 分析化学 · 环境科学 · 医学
✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY · 2022 ·Vol. 38 ·期 1 ·142-155 · IF 4.351

High-precision double-spike Sn isotope analysis of geological materials by MC-ICP-MS

Jia-Xin She,Weiqiang Li,Shichao An,Yuanfeng Cai

Stable Sn isotopes have the potential to constrain the behavior of Sn in various natural and anthropogenetic processes, however, studies on stable isotopes of Sn for terrestrial rock samples have been limited. Here, we present a high-precision Sn isotope analytical method of geological samples by the double spike technique. Samples were equilibrated with a 117Sn–122Sn double spike during dissolution, then Sn was purified from the rock matrix using TRU spec resin. The purified Sn solutions were analyzed on a Nu 1700 Sapphire MC-ICP-MS, and data reduction was performed using Newton–Raphson iteration. Effects of acid mismatch, concentration mismatch, and matrix elements were systematically tested to evaluate their impact on the accuracy and repeatability of the measurements. We show that the mismatch of acidity exerts negligible influences on the Sn isotope analysis. By contrast, the accuracy of Sn isotopic measurements could be compromised if the Sn concentration of the sample is below 40% of that of the standard. To ensure the accuracy of Sn isotope analysis, the concentration match between the sample and standard should be better than ±20%. When the measured solution has varying mass ratios of [X]/Sn (ng g−1/ng g−1) lower than 0.5 for Mg, Ca, Fe, Ti, U, Ni, Ag, As, Ru, and Mo, the measured Sn isotope composition was not affected. However, Cd in Sn samples could affect the accuracy of Sn isotope analysis by the 117Sn–122Sn double spike through the generation of 116CdH+ in plasma that interferes with 117Sn+. The Cd/Sn ratio needs to be below 0.01 to ensure analytical accuracy by the double spike method. The accuracy of this method was further verified by measuring the pure solution with both double spike and sample standard bracketing methods, as well as processing a synthetic solution through column chemistry. The Sn isotope compositions of geological samples measured using our method are reproducible and consistent with previous data from other laboratories. Additionally, Sn isotope data for geological reference materials BIR-1, RGM-1, and GSR-1 are reported for the first time. Based on repeated analyses of pure and geological reference materials, the long-term intermediate precision is better than ±0.069‰ on δ122/118Sn for a spiked solution of 100 μg g−1.

研究领域: 地球化学 · 分析化学 · 地质学
✓ 已验证 DOI 高影响因子
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ELECTROPHORESIS · 2020 ·Vol. 42 ·期 4 ·465-472 · IF 3.081

Ti (IV) modified vinyl phosphate magnetic nanoparticles for simultaneous preconcentration of multiple arsenic species from chicken samples followed by HPLC-ICP-MS analysis

Qiuyue Xu,Beibei Chen,Man He,Bin Hu

Ti (IV)-modified vinyl phosphate magnetic nanoparticles (Fe 3 O 4 @SiO 2 @KH570-PO 4 -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 Fe 3 O 4 @SiO 2 @KH570-PO 4 -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.

研究领域: 分析化学 · 环境科学 · 食品科学
✓ 已验证 DOI 高影响因子
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SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY · 2024 · IF 3.2

Selective extraction and determination of trace metals by magnetic covalent organic frameworks with abundant thione and secondary amine groups coupled with ICP-MS

Yinzhong Gao,Heping Jiao,Zhenhua Wang,Jingbo Chao,Jian Li,Ligang Hu,Shengxiao Zhang,Jing Sun

A core-shell magnetic covalent organic frameworks (MCOF-SN) nanocomposite with high adsorption capacity was prepared by simply and directly coating covalent organic frameworks with abundant thione and secondary amine groups on the surface of magnetic nanoparticles, which were used to selectively extract copper (Cu 2+ ), cadmium (Cd 2+ ), lead (Pb 2+ ), cobalt (Co 2+ ) and nickel (Ni 2+ ) ions prior to the detection by ICP-MS. The prepared magnetic covalent organic frameworks have high adsorption capacity of 52, 65, 162, 34 and 42 mg g −1 for Cu 2+ , Cd 2+ , Pb 2+ , Co 2+ and Ni 2+ ions, respectively. The analytical parameters affecting magnetic solid-phase extraction (MSPE) of metal ions were optimized. They were pH of sample, 4–5; eluent, 1 mL of 1 % ( v /v) HNO 3 ; amount of adsorbent, 15 mg; and sample volume, 200 mL. Under optimal experimental conditions, the limits of detection (LODs) of Cu 2+ , Cd 2+ , Pb 2+ , Co 2+ and Ni 2+ ions for water are 0.26, 0.16, 0.25, 0.08 and 0.17 ng L −1 with enrichment factors of 192, 191, 196, 188 and 190, and their relative standard deviations (RSD) were less than 5 % (20 ng L −1 , n  = 3), respectively. The LODs for Chinese herbal medicine samples were 0.52, 0.32, 0.50, 0.16 and 0.34 μg kg −1 based on 0.100 g sample, respectively. The proposed MSPE-inductively coupled plasma mass spectrometry (MSPE-ICP-MS) method with simple operation, high sensitivity and high anti-matrix interference ability has been successfully applied to the samples with complicated matrices, such as water and Chinese herbal medicine.

CAS / MDL: 919-30-2 108-67-8
研究领域: 分析化学 · 环境科学
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