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ANALYTICAL CHEMISTRY · 2018 · IF 6.042

Highly Sensitive Detection of MicroRNA-21 with ICPMS via Hybridization Accumulation of Upconversion Nanoparticles

Xun Liu,Shang-Qing Zhang,Zi-Han Cheng,Xing Wei,Ting Yang,Yong-Liang Yu,Ming-Li Chen,Jian-Hua Wang

A highly sensitive platform is developed for the determination of microRNA-21 (miRNA-21) with inductively coupled plasma mass spectrometry (ICPMS). It includes the following operations: Hairpin structures DNA H1 and H2 are designed, and DNA H1 is bound to ultrasmall lanthanide upconversion nanoparticles (UCNPs) to produce UCNPs@DNA conjugate probes. Target miRNA triggers a chain reaction for alternating hybridization between DNA H1 (bound on UCNPs@DNA probe) and DNA H2. This leads to UCNPs accumulation and serves as an efficient amplification strategy for UCNPs. The concentration of miRNA-21 is closely correlated to the number of UCNPs; thus, the detection of 89Y by ICPMS provides a promising approach for miRNA quantification. This protocol exhibits high sensitivity to miRNA-21 within 0.1–500 fM, along with a detection limit of 41 aM, which is among the hitherto reported most sensitive procedures. It is worth mentioning that rare earth elements are scarcely present in living systems, which minimizes the background for ICPMS detection and excludes potential interferences from the coexisting species, which is most suited for biological assay.

研究领域: 生物化学 · 分析化学 · 分子生物学
✓ 已验证 DOI PubMed 高影响因子
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ANALYTICA CHIMICA ACTA · 2019 · IF 5.256

Single cell analysis for elucidating cellular uptake and transport of cobalt curcumin complex with detection by time-resolved ICPMS

Qi-Xuan Sun,Xing Wei,Shang-Qing Zhang,Ming-Li Chen,Ting Yang,Jian-Hua Wang

It is of great importance to elucidate the fate of drugs, e.g., their cellular uptake, transport and metabolism/excretion at single cell level. In the present work, cellular uptake and excretion of curcumin in HepG2 and MCF-7 cells were investigated by measuring 59 Co in a curcumin cobalt complex ([Co(tpa)(cur)](ClO 4 ) 2 ) with inductively coupled plasma mass spectrometry (ICPMS). The uptake and distribution pattern of the metal drug complex in single cells were thoroughly studied, demonstrating extremely large discrepancy of uptake behavior among individual cells. The complex concentration-dependent uptake and excretion behavior is observed for both HepG2 and MCF-7 cells. The uptake of ([Co(tpa)(cur)](ClO 4 ) 2 ) by HepG2 cells is firstly increased with the concentration of the complex followed by level-off at certain level. On the other hand, however, the uptake by MCF-7 cells increases exponentially with the complex concentration within a same concentration range. The present study provides important information on the transport process of the metal drug complex at single cell level, it may be promising for further applications in the elucidation of metal drug effectiveness in vivo.

研究领域: 药物代谢 · 细胞生物学 · 分析化学
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ANALYTICAL CHEMISTRY · 2015 · IF 5.636

Hydrophilic Polymer Monolithic Capillary Microextraction Online Coupled to ICPMS for the Determination of Carboxyl Group-Containing Gold Nanoparticles in Environmental Waters

Lin Zhang,Beibei Chen,Man He,Xiaolan Liu,Bin Hu

In this study, the hydrophilic polymer monolithic capillary (poly(acrylamide-vinylpyridine-methylene bis(acrylamide)), poly(AA-VP-Bis)) was prepared for the separation and enrichment of carboxyl group-containing gold nanoparticles (Au NPs) from environmental waters followed by online ICPMS determination. The extraction mechanism of the prepared poly(AA-VP-Bis) monolithic capillary for Au NPs is based on the static electrical and hydrogen bond interactions between the carboxyl group on the surface of Au NPs and pyridine/amide groups on the surface of the monolith. Under the optimal conditions, a detection limit of 24.2 fmol L–1 and a sample throughput of 6 h–1 were achieved for 3 nm citrate stabilized Au NPs, and the original morphology of the Au NPs could be maintained during the extraction process. The developed method was successfully applied for the analysis of carboxyl group-containing Au NPs in environmental water samples, such as tap water, the Yangtze River water, and the East Lake water, with recoveries in the range of 77–103%. Compared with the reported approaches for analysis of Au NPs, this method is an online strategy for carboxyl group-containing Au NPs determination and has the merits of low detection limit, small sample consumption, fast extraction/desorption kinetics, wide linear range, high selectivity, and high throughput.

研究领域: 分析化学 · 环境科学
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ANALYTICAL CHEMISTRY · 2018 · IF 6.042

Facile Design of Phase Separation for Microfluidic Droplet-Based Liquid Phase Microextraction as a Front End to Electrothermal Vaporization-ICPMS for the Analysis of Trace Metals in Cells

Xiaoxiao Yu,Beibei Chen,Man He,Han Wang,Songbai Tian,Bin Hu

The issue of quantifying trace metals in cells has drawn widespread attention but is threatened with insufficient sensitivity of the instruments, complex cellular matrix and limited cell consumption. In this study, microfluidic droplet-based liquid phase microextraction (LPME), as a miniaturized platform, was developed and combined with electrothermal vaporization (ETV)-inductively coupled plasma mass spectrometry (ICPMS) for the analysis of trace Cd, Hg, Pb, and Bi in cells. A novel and facile design of phase separation region was proposed, which made the phase separation very easily for subsequent ETV-ICPMS detection. Mechanism of the phase separation was carefully discussed using the incompressible formulation of the Navier–Stokes equations. The developed microfluidic droplet-based LPME system exhibited much higher extraction efficiency to target metals than microfluidic stratified flow-based LPME. Under the optimized conditions, the limits of detection of the proposed microfluidic droplet-based LPME-ETV-ICPMS system were 2.5, 3.9, 5.5, and 3.4 ng L–1 for Cd, Hg, Pb, and Bi, respectively. The accuracy of the developed method was well validated by analyzing the target metals in Certified Reference Materials of GBW07601a human hair. Finally, the proposed method was successfully applied to the analysis of target metals in HeLa and HepG2 cells with the recoveries for the spiked samples ranging from 83.5 to 112.3%. Overall, the proposed design is a simple and reliable solution for the phase separation on droplet-chip and the microfluidic droplet-based LPME-ETV-ICPMS combination strategy shows great promise for trace elements analysis in cells.

研究领域: 分析化学 · 环境科学 · 生物医学工程
✓ 已验证 DOI PubMed 高影响因子
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Real-time monitoring of culture medium- and species-specific transformation of zinc oxide nanoparticles in bacterial systems using coupled CyElFFF-ICPMS

Weichen Zhao,Zhangguo Wu,Meseret Amde,Hongwei Liu,Yan Li,Quanlong Wang,Yongguang Yin,Maoyong Song,Zhiqiang Tan,Yukui Rui,Qinghua Zhang,Bruce K. Gale,Guibin Jiang

Zinc oxide nanoparticles (ZnO NPs) have emerged as promising nanoagrochemicals due to their high utility and efficiency. For the first time, we employed an online-coupled cyclical electrical field-flow fractionation and inductively coupled plasma mass spectrometry (CyElFFF-ICPMS) system for rapid (<10 min) simultaneous characterization and quantification of ZnO NPs and Zn(II) ions in aqueous matrices, achieving a detection limit of 0.03 μg/mL and 92 % recovery. CyElFFF-ICPMS analysis demonstrated that ZnO NPs remain well-dispersed in ultrapure water but formed surface coronas in yeast mannitol broth prior to precipitation, demonstrating culture medium-specific stability profiles. Crucially, we observed divergent transformation mechanisms between beneficial bacteria. Gram-positive bacteria ( Bacillus subtilis ) stabilized ZnO NPs via biomolecular corona formation, while Gram-negative bacteria ( Sinorhizobium fredii ) promoted extracellular ZnO NPs aggregation and dissolution via protein-rich extracellular polymeric substance secretion, as validated by 3D excitation-emission matrix fluorescence spectroscopy. Intracellular transformation diverged markedly after 6 h: B. subtilis reduced internalized Zn(II) to ZnO nanocomposites through activated the detoxification mechanism, contrasting with S. fredii 's extensive intracellular dissolution and extracellular precipitation. These findings demonstrate that bacterial species-specific interactions critically govern the stability, transformation, and intracellular fate of ZnO NPs, providing essential mechanistic insights imperative for rational design of nanoagrochemicals and their environmental risk assessment.

研究领域: 环境纳米技术 · 微生物学 · 分析化学 · 纳米毒理学 · 农业化学品
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2021 ·Vol. 413 ·期 5 ·1353-1361 · IF 4.157

Dual-mode imaging of copper transporter 1 in HepG2 cells by hyphenating confocal laser scanning microscopy with laser ablation ICPMS

Sun Qi-Xuan,Wei Xing,Zhang Shang-Qing,Chen Ming-Li,Yang Ting,Yu Yong-Liang,Wang Jian-Hua

Copper transporter 1 (CTR1) is a transport protein involved in copper and cisplatin uptake. The visualization of cellular CTR1 migration and its redistribution is highly important in copper/cisplatin exposure/transport. However, to the best of our knowledge, this is a highly challenging task. Herein, a dual-mode imaging strategy for CTR1 is developed by hyphenating confocal laser scanning microscopy (CLSM) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) with a fluorescent/elemental bifunctional tag conjugated with anti-CTR1 antibody. The tag consists of rhodamine B and zirconium metal-organic frameworks (Zr-MOF) for CLSM fluorescence imaging and LA-ICPMS element imaging for a same group of HepG2 cells in a designated visual zone. This dual-mode imaging strategy facilitates visualization of CTR1 migration and meanwhile provides information of CTR1 redistribution in HepG2 cells by uptake of divalent copper or cisplatin. The present dual-mode imaging strategy provides in-depth information for the elucidation of CTR1 involved biological processes. Graphical abstract

研究领域: 生物学 · 生物化学 · 分析化学 · 细胞生物学 · 药理学
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2017 ·Vol. 315 ·期 1 ·103-110 · IF 1.282

Rapid method for accurate determination of actinides (U, Th, Pu and Am) in water samples for emergency response

Wang Zhongtang,Lin Jinxian,Li Sixuan,Guo Qiuju,Huang Wenna,Wen Wei,Dan Guiping,Tan Zhaoyi

To rapidly assess the contamination of actinides in emergency water, a method was developed to simultaneously analyze U, Th, Pu and Am. The method consists of two steps: extraction chromatographic separation using UTEVA and DGA resins and isotopic determination of actinides by inductively coupled plasma mass spectrometry (ICPMS). The whole analytical procedure takes only 8 h and high chemical recoveries of actinides were obtained. The cross spectral interferences between actinides in ICPMS measurement were sufficiently removed. The accuracy was validated by analyzing IAEA-443 seawater sample. The low limits of detection of actinides allow this method to distinguish low level contamination.

研究领域: 环境科学 · 核化学
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ANALYTICAL CHEMISTRY · 2019 · IF 6.35

Intracellular Zinc Quantification by Fluorescence Imaging with a FRET System

Yang Shu,Na Zheng,An-Qi Zheng,Ting-Ting Guo,Yong-Liang Yu,Jian-Hua Wang

Fluorescence imaging of cellular metals is widely reported. However, the quantification of intracellular metals with fluorescence imaging is so far not feasible and highly challenging. In this work, a ratiometric probe with two fluorescently labeled complementary DNA strains is designed for intracellular zinc quantification via fluorescence imaging, based on fluorescence resonance energy transfer (FRET) from carbon dots (CDs) to fluorescein (FAM). The donor CDs are modified with a Zn2+ aptamer, whereas the receptor FAM is conjugated with the complementary DNA sequence to ensure selectivity. MCF-7 cells are cultured sequentially with Zn2+ (20, 40, 55, 70, 85, and 100 μmol L–1) and CDs–FAM (100 μg mL–1), which is used for fluorescence imaging (at λex = 405 nm and λem = 440–490 nm for CDs, λem = 500–550 nm for FAM) to provide a relative fluorescence ratio ((F – F0)/F0, F = ICDs/IFAM), followed by quantifying intracellular zinc with ICPMS. A linear correlation is achieved between the relative fluorescence ratio in fluorescence images and the intracellular zinc content derived by ICPMS, which facilitates intracellular zinc quantification via fluorescence imaging. It is especially useful for real-time tracing of intracellular zinc during the cell culturing process or in vivo. The cellular uptake of Zn2+ by MCF-7 cells is further evaluated with this approach by culturing with 100 μmol L–1 of Zn2+ for different times, and a maximum uptake of 60.5 fg per cell is observed at an incubation time of 60 min. This value is further demonstrated well by ICPMS detection.

CAS / MDL: 25952-53-8 6066-82-6
研究领域: 分析化学 · 细胞生物学 · 生物医学工程 · 材料科学
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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Species-specific Antimony Isotope Analysis by High Performance Liquid Chromatography Coupled with Multicollector ICPMS Using Hydride Generation as an Interface

Linjie Chen,Yuanyuan Du,Shuyang Li,Xing Liu,Jun Shen,Zhenli Zhu

A novel method has been developed for the simultaneous online determination of the isotopic compositions of different antimony (Sb) species in a single analytical run using high-performance liquid chromatography (HPLC) coupled with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), with hydride generation (HG) serving as the interface. Various parameters affecting the precision of Sb isotope analysis including HG conditions, transient signal processing methods and peak integration windows, were optimized. The linear regression slope method and a 100% peak integration window provided the optimal precision. Under optimized conditions, our method achieved external 2SD precisions better than 0.05‰ for both Sb(III) and Sb(V), with minimal consumption of 0.5 ng for Sb(III) and 5 ng for Sb(V). Furthermore, flow injection (FI) coupled with HG-MC-ICPMS demonstrated precise Sb isotopic analysis with sample requirements as low as 0.25 ng. The proposed methods were validated by analyzing δ123Sb in synthetic solutions and reference materials. Additionally, it was applied to investigate isotopic fractionation during the reduction of Sb(V) by KI, revealing preferential reduction of the light Sb isotope(121Sb). The isotopic compositions of Sb(V) varied from −0.04– 1.18‰, fitting well with a Rayleigh fractionation model and yielding a fractionation factor (αSb(III)–Sb(V)) of 0.99831. In summary, this approach enables high precision isotopic analysis of Sb(III) and Sb(V) simultaneously with reduced sample consumption, providing a powerful tool for investigating Sb isotopic fractionation in various environmental processes and advancing our understanding of the Sb biogeochemical cycle.

研究领域: 环境科学 · 分析化学
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ANALYTICAL CHEMISTRY · 2017 · IF 6.32

Facile Chip-Based Array Monolithic Microextraction System Online Coupled with ICPMS for Fast Analysis of Trace Heavy Metals in Biological Samples

Jing Zhang,Beibei Chen,Han Wang,Man He,Bin Hu

Trace heavy metals have great impact on biological system; therefore, it is essential to develop suitable analytical methods for the determination of trace heavy metals in biological samples to elucidate their biochemical and physiological functions in organisms. Herein, we presented a chip-based array monolithic microextraction system and combined it with inductively coupled plasma mass spectrometry (ICPMS) for online analysis of trace Hg, Pb, and Bi in real-world biological samples. Six ethylenediamine modified poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly(GMA-co-EDMA-NH2)) capillary monolithic columns were embedded parallelly in microchannels of a microfluidic chip for array monolithic microextraction. Various parameters affecting the chip-based array monolithic microextraction of target metals were investigated. The sample throughput of the proposed method was 16 h–1, with the limits of detection for Hg, Pb, and Bi of 23, 12, and 13 ng L–1, respectively. The developed method was validated by the determination of trace Hg, Pb, and Bi in HepG2 cells and human urine samples, and the recoveries for the spiked samples were in the range of 90.4–102%. This chip-based array monolithic microextraction system is easy to prepare, and the proposed online analytical system provides a new platform for trace elements analysis in biological samples with the merits of high sample throughput, high sensitivity, and low sample/reagents consumption.

CAS / MDL: 108-93-0 112-53-8
研究领域: 分析化学 · 环境科学 · 生物医学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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FOOD CHEMISTRY · 2021 · IF 7.514

Ultrasensitive determination and non-chromatographic speciation of inorganic arsenic in foods and water by photochemical vapor generation-ICPMS using CdS/MIL-100(Fe) as adsorbent and photocatalyst

Manlu Wang,Juan He,Jin Luo,Jing Hu,Xiandeng Hou

The determination of inorganic arsenic species in real samples can be particularly challenging due to their trace levels and the interferences arising from sample matrix. Normally, the speciation analysis necessitates chromatographic separation. Herein, we report a novel method for the ultrasensitive detection and non-chromatographic speciation of inorganic arsenic by inductively coupled plasma mass spectrometry (ICP-MS), utilizing CdS/MIL-100(Fe) composites as an adsorbent and photocatalyst. The synthesized CdS/MIL-100(Fe) could completely adsorb As(V) and As(III) within 5 and 105 min, respectively. Following filtration and re-suspension in formic acid, the adsorbed As(III)/As(V) were reduced to arsine (AsH 3 ) under UV irradiation and swept to ICP-MS for detection. The limits of detection were found to be 1.7 ng L −1 (without preconcentration) and 0.11 ng L −1 (after 20-fold preconcentration). The method was successfully applied to the determination of trace inorganic arsenic in various food and water samples.

研究领域: 分析化学 · 环境科学 · 食品科学
✓ 已验证 DOI PubMed 高影响因子
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 411 ·期 18 ·4193-4202 · IF 3.286

Fluorescent and mass spectrometric evaluation of the phagocytic internalization of a CD47-peptide modified drug-nanocarrier

Liu Chunlan,Yu Danxia,Ge Fuchun,Yang Limin,Wang Qiuquan

Ru(bpy) 3 @SiO 2 -COOH and Ru(bpy) 3 @SiO 2 @CD47-peptide nanoparticles (NPs) with fluorescent and mass spectrometric properties were designed and synthesized as the models of drug-nanocarriers. Their phagocytic internalization could be quantitatively measured using more sensitive inductively coupled plasma mass spectrometry (ICPMS) ( 102 Ru) versus traditional laser confocal scanning microscope ( λ ex/em  = 458/600 nm) for the first time. Modification of a self-signal trigging CD47-peptide on the NPs’ surface decreased internalization by 10 times, (2.79 ± 0.21) × 10 4 Ru(bpy) 3 @SiO 2 -COOH and (0.28 ± 0.04) × 10 4 Ru(bpy) 3 @SiO 2 @CD47-peptide NPs per RAW264.7 macrophage ( n  = 5). The alkynyl-linked CD47-peptide allowed us to quantify the number (2412 ± 250) of CD47-peptide modified on the NP and the total content (5.14 ± 0.25 amol) of signal regulatory protein α (SIRPα) on the macrophage by measuring the clickable tagged Eu using ICPMS. Furthermore, the interaction between CD47-peptide and SIRPα as well as the changes of the remaining free SIRPα during the internalization process of Ru(bpy) 3 @SiO 2 @CD47-peptide NPs were quantitatively evaluated, providing direct experimental evidence of the longspeculated crucial CD47-SIRPα interaction for drug-nanocarriers to escape internalization by phagocytic cells. Remarkable difference in the internalization ratio of 12.3 ± 4.8 of Ru(bpy) 3 @SiO 2 -COOH NPs and 4.3 ± 0.5 Ru(bpy) 3 @SiO 2 @CD47-peptide NPs with and without the protein corona indicated that CD47-peptide still worked when the protein corona formed. Not limited to the evaluation of the NPs studied here, such a fluorescent and mass spectrometric approach is very much expected to apply to the assessment of other drug-nanocarriers designed by chemists and before their medical applications. Graphical abstract

研究领域: 纳米技术 · 药理学 · 生物医学工程 · 分析化学
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