World Congress on Biosensors 2014

World Congress on Biosensors 2014
Biosensors 2014

Tuesday, 9 October 2012

Analytica Chimica Acta

A new issue of this journal has just been published. To see abstracts of the papers it contains (with links through to the full papers) click here:
Selected papers from the latest issue:

Silicon nanowire biosensor and its applications in disease diagnostics: A review

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
Guo-Jun Zhang, Yong Ning
Over the past decade, silicon nanowire (SiNW) biosensors have been studied for the detection of biological molecules as highly sensitive, label-free, and electrical tools. Herein we present a comprehensive review about the fabrication of SiNW biosensors and their applications in disease diagnostics. We discuss the detection of important biomarkers related to diseases including cancer, cardiovascular diseases, and infectious diseases. SiNW biosensors hold great promise to realize point-of-care (POC) devices for disease diagnostics with potential for miniaturization and integration.

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A typical SiNW FET-based biosensor for detecting biomolecules.
► SiNW biosensor has been developed as a sensitive, label-free, electrical tool. ► SiNW biosensor has been applied to the detection of important biomarkers. ► SiNW biosensor shows a potential of miniaturization and integration. ► SiNW biosensor indicates a promising POC device for disease diagnostics. ► The diseases can include cancer, cardiovascular disease, and infectious disease.

Carbon nanotubes as solid-phase extraction sorbents prior to atomic spectrometric determination of metal species: A review

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
C. Herrero Latorre, J. Álvarez Méndez, J. Barciela García, S. García Martín, R.M. Peña Crecente
New materials have significant impact on the development of new methods and instrumentation for chemical analysis. From the discovery of carbon nanotubes in 1991, single and multi-walled carbon nanotubes – due to their high adsorption and desorption capacities – have been employed as sorption substrates in solid-phase extraction for the preconcentration of metal species from diverse matrices. Looking for successive improvements in sensitivity and selectivity, in the past few years, carbon nanotubes have been utilized as sorbents for solid phase extraction in three different ways: like as-grown, oxidized and functionalized nanotubes. In the present paper, an overview of the recent trends in the use of carbon nanotubes for solid phase extraction of metal species in environmental, biological and food samples is presented. The determination procedures involved the adsorption of metals on the nanotube surface, their quantitative desorption and subsequent measurement by means of atomic spectrometric techniques such as flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry/mass spectrometry, among others. Synthesis, purification and types of carbon nanotubes, as well as the diverse chemical and physical strategies for their functionalization are described. Based on 140 references, the performance and general properties of the applications of solid phase extraction based on carbon nanotubes for metal species atomic spectrometric determination are discussed.

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► The use of CNTs as sorbent for metal species in solid phase extraction has been described. ► Physical and chemical strategies for functionalization of carbon nanotubes have been discussed. ► Published analytical methods concerning solid phase extraction and atomic spectrometric determination have been reviewed.

Comparison of two lab-made spray chambers based on MSIS™ for simultaneous metal determination using vapor generation-inductively coupled plasma optical emission spectroscopy

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
A. Fuentes-Cid, J. Villanueva-Alonso, E. Peña-Vázquez, P. Bermejo-Barrera
The objective of this study is to evaluate the performance of two lab-made systems based on the Multimode Introduction System (MSIS™) and the modified MSIS™, to generate and introduce vapors of Ag, Cu, Cd, Cu, Ni, Sn, Zn, and also Au in the ICP torch. An univariate procedure was used to select the optimized working conditions (Ar flow, sample, reductant and waste flows, and reagent concentrations). Optimum conditions for working with modified MSIS were: nitric acid concentration 0.35M, 8-hydroxyquinoline concentration: 40mgL−1, sodium borohydride concentration: 1.75% (w/v)+0.4% (w/v) NaOH, argon purge flow to sweep the vapors to the torch: 1.2Lmin−1, sample flow and sodium borohydride flows: 2.3Lmin−1; waste flow: 7.7mLmin−1. For the optimum working conditions for lab-made MSIS in dual mode the concentration of 8-hydroxyquinoline was 225mgL−1, the Ar purge flow was 0.75Lmin−1, and the conventional nebulization flow was 2.3Lmin−1. The sensitivity obtained was higher using the lab-made MSIS than using the lab-made modified MSIS or a forced outlet gas–liquid separator. The limits of detection were better for Au, Cd, Sn than those obtained using conventional nebulization; the measurements were precise (RSDs≤5% in dual mode) and a good accuracy was obtained in the determination of Cd, Cu, Ni and Zn in a wastewater reference material using aqueous calibration and the lab-made MSIS in dual mode.

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Graphical abstract Highlights

► Two lab-made systems based on MSIS™ were evaluated to generate vapors of Ag, Au, Cd, Cu, Ni, Sn and Zn. ► The present study provides data about Au in a dual-mode sample-introduction system. ► The two systems were compared with the use of a forced outlet gas–liquid separator and conventional nebulization. ► The LODs were lower for Au, Cd and Sn using lab-made MSIS working in dual mode. ► 8-Hydroxyquinoline was used to improve volatilization, and detection was performed by ICPOES.

A new beryllium ion-selective membrane electrode based on dibenzo(perhydrotriazino)aza-14-crown-4 ether

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
Vinod Kumar Gupta, Ashok Kumar Singh, Naveen Mergu
Beryllium(II) selective electrodes have been fabricated based on poly(vinyl chloride) (PVC) matrix membranes containing newly synthesized neutral carrier dibenzo(perhydrotriazino)aza-14-crown-4 ethers as ionophore. Best performance was exhibited by the membrane having a composition ionophore (IIa):PVC:sodium tetraphenylborate (NaTPB):tributyl phosphate (TBP) in the ratio (w/w; mg) of 5:30:3:65. This membrane worked well over a wide concentration range 7.6×10−6 to 1.0×10−1 M of Be2+ with a Nernstian slope of 30.7mV per decade of beryllium activity. The response time of the sensor is 15s and the membrane can be used over a period of 4months with good reproducibility. The proposed electrode works well in a wide pH range 3.0–9.0. It was successfully applied to the determination of beryllium in a mineral sample.

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Variation of potential with Be2+ activity for membrane sensors based on dibenzo(perhydrotriazino)aza-14-crown-4 ether.
► It is the first report on an ion sensor using substituted aza-14-crown-4 for Be2+. ► Response time is 15s and life time is more than 4months with good reproducibility. ► The proposed electrode works well in a wide pH range 3.0–9.0.

Development of an extraction method for the determination of prostaglandins in biological tissue samples using liquid chromatography–tandem mass spectrometry: Application to gonads of Atlantic cod (Gadus morhua)

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
Steve Janagap, Rita Azeredo, Thu-Thao Nguyen, Kristin Hamre, Pedro Araujo
A simple extraction method for the analysis of PGE2 and PGF2α in gonad samples from Atlantic cod and further quantification by using liquid chromatography–tandem mass spectrometry is proposed. The evaluation of the best solvent extraction conditions and the analytical performance parameters are reported. The method was highly selective for both prostaglandins and the calibration curves, based on the internal standard method, were linear between 5 and 1000ngmL−1 for PGE2 and PGF2α, with limits of detection of 1ngmL−1 and 1.5ngmL−1 and recovery values of 99.999±0.002 and 99.967±0.023 respectively. The homogenization of samples using liquid nitrogen combined with the developed extraction protocol can be implemented in different types of biological tissues.

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► Novel method for extraction of prostaglandins from fish gonads using LC–MS/MS. ► Key features: low sample and solvent consumption and high sample throughput. ► The method is a better alternative to ELISA generally used in reproduction studies.

Polyethyleneimine-capped silver nanoclusters as a fluorescence probe for sensitive detection of hydrogen peroxide and glucose

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
Ting Wen, Fei Qu, Nian Bing Li, Hong Qun Luo
In this work, we utilized polyethyleneimine-capped silver nanoclusters (PEI-Ag nanoclusters) to develop a new fluorometric method for the determination of hydrogen peroxide and glucose with high sensitivity. The PEI-Ag nanoclusters have an average size of 2nm and show a blue emission at 455nm. The photostable properties of the PEI-Ag nanoclusters were examined. The fluorescence of the PEI-Ag nanoclusters could be particularly quenched by H2O2. The oxidization of glucose by glucose oxidase coupled with the fluorescence quenching of PEI-Ag nanoclusters by H2O2 can be used to detect glucose. Under optimum conditions, the fluorescence intensity quenched linearly in the range of 500nM–100μM with high sensitivity. The detection limit for H2O2 was 400nM. And a linear correlation was established between fluorescence intensity (F 0 − F) and concentration of glucose in the range of 1.0×10−6 to 1.0×10−5 M and 1.0×10−5 to 1.0×10−3 M with a detection limit of 8.0×10−7 M. The method was used for the detection of glucose in human serum samples with satisfactory results. Furthermore, the mechanism of sensitive fluorescence quenching response of Ag nanoclusters to glucose and H2O2 has been discussed.

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Graphical abstract Highlights

► A new method for synthesis of Ag nanoclusters using polyethyleneimine as a stabilizing agent was developed. ► Water-soluble Ag nanoclusters possessed high fluorescence and excellent biocompatibility. ► A new approach for determination of glucose and H2O2 by fluorescence quenching was developed. ► The method for detecting glucose and H2O2 has high sensitivity, low toxicity, and easy operation. ► Ag nanoclusters has great potential for bioimaging.

Acid dissociation constants of uridine-5′-diphosphate compounds determined by 31phosphorus nuclear magnetic resonance spectroscopy and internal pH referencing

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
Igor Jancan, Megan A. Macnaughtan
The acid dissociation constant (pK a) of small, biological molecules is an important physical property used for investigating enzyme mechanisms and inhibitor design. For phosphorus-containing molecules, the 31P nuclear magnetic resonance (NMR) chemical shift is sensitive to the local chemical environment, particularly to changes in the electronic state of the molecule. Taking advantage of this property, we present a 31P NMR approach that uses inorganic phosphate buffer as an internal pH reference to determine the pK a values of the imide and second diphosphate of uridine-5′-diphosphate compounds, including the first reported values for UDP-GlcNAc and UDP-S-GlcNAc. New methods for using inorganic phosphate buffer as an internal pH reference, involving mathematical correction factors and careful control of the chemical shift reference sample, are illustrated. A comparison of the newly determined imide and diphosphate pK a values of UDP, UDP-GlcNAc, and UDP-S-GlcNAc with other nucleotide phosphate and thio-analogs reveals the significance of the monosaccharide and sulfur position on the pK a values.

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Graphical abstract Highlights

► The first reported phosphate and imide pK a values of UDP-GlcNAc and UDP-S-GlcNAc. ► New role for the monosaccharide in the imide pK a of uridine-5′-phosphate compounds. ► UDP-S-GlcNAc and UDP-GlcNAc have the same phosphate pK a, unlike thioyl analogs. ► The 31P chemical shift of inorganic phosphate is a viable internal pH reference. ► Stability of the external 31P chemical shift reference is essential.

Label-free and fluorescence turn-on aptasensor for protein detection via target-induced silver nanoclusters formation

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 749
Jing-Jing Liu, Xiao-Rong Song, Yi-Wei Wang, Ai-Xian Zheng, Guo-Nan Chen, Huang-Hao Yang
A simple turn-on and homogeneous aptasensor, which relies on target induced formation of silver nanoclusters (Ag NCs), was developed for the determination of platelet-derived growth factor B-chain homodimer (PDGF-BB). The aptasensor contains two hairpin DNA probes termed as P1 and P2. P1 consists of the aptamer sequence of PDGF-BB. Meanwhile, P2 contains the Ag NCs nucleation sequence, which is blocked by the hairpin stem region. P1 and P2 can co-exist metastably in the absence of PDGF-BB and maintain hairpin structure. However, in the presence of PDGF-BB, the binding of PDGF-BB with aptamer will result in the hybridization between P1 and P2, and release the Ag NCs nucleation sequence. In this case, Ag NCs can be formed via the reduction of Ag+ by NaBH4. By monitoring the increase in fluorescence intensity, we could detect the target protein with high sensitivity. The detection limit of this aptasensor is 0.37nM, which is comparable with that of other reported aptasensors. Furthermore, this proposed aptasensor shows high selectivity toward its target protein. Thus, the proposed aptasensor based on target induced formation of Ag NCs could be used as a sensitive and selective platform for the detection of target protein.

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Graphical abstract Highlights

► A turn-on aptasensor was developed via target induced silver nanoclusters formation. ► This aptasensor exhibited high sensitivity and selectivity for PDGF-BB detection. ► This aptasensor is capable of detecting PDGF-BB in real samples. ► This aptasensor is label-free, making it more simple and cost effective.

Preparation of molecularly imprinted polymers for organophosphates and their application to the recognition of organophosphorus compounds and phosphopeptides

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 748
Jun Haginaka, Hiromi Tabo, Hisami Matsunaga
Monodisperse molecularly imprinted polymers (MIPs) for diphenyl phosphate (DPP) and 1-naphthyl phosphate (1-NapP) have been prepared by a multi-step swelling and polymerization method using 4-vinylpyridine as a functional monomer, glycerol dimethacrylate as a crosslinker and cyclohexanol or 1-hexanol as a porogen. The retention and molecular-recognition properties of these MIPs for organophosphorus compounds were evaluated by HPLC using a mixture of phosphate buffer and acetonitrile as an eluent. In addition to shape recognition, hydrogen bonding and hydrophobic interactions could play an important role in the retention and molecular recognition of DPP and 1-NapP. Furthermore, the MIPs were applied to the separation of adenosine and adenosine phosphates (AMP, ADP and ATP). These phosphates were retained on the MIPs according to the number of phosphate groups in the molecule and were well separated from one another. Hydrogen bonding and hydrophobic interactions seemed to affect the retention and recognition of adenosine phosphates in low acetonitrile content, while hydrophilic interactions affected these properties in high acetonitrile content. Finally, the MIPs were applied to the trapping of phosphopeptides. The MIPs non-selectively trapped phosphopeptides, which have phosphorylated tyrosine, serine or threonine in the sequences, and successfully trapped four phosphopeptides in tryptic digests of bovine α-casein.

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Graphical abstract Highlights

► Monodisperse MIPs for organophosphates by multi-step swelling and polymerization. ► Application of MIPs to the separation of adenosine phosphates. ► Application of MIPs to the trapping of phosphopeptides in tryptic protein-digests.

Application of semi-permeable membrane dialysis/ion trap mass spectrometry technique to determine polybrominated diphenyl ethers and polychlorinated biphenyls in milk fat

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 748
Marek Roszko, Małgorzata Rzepkowska, Arkadiusz Szterk, Krystyna Szymczyk, Renata Jędrzejczak, Marcin Bryła
Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are hazardous food contaminants, their maximum legally allowable levels in food and environment are in the low pgg−1 range. Therefore some highly selective and sensitive analytical methods must be used to determine them. The 96/23/EC Directive implemented by EC Decision of 12 August 2002 requires recovery rate of an analyte at a concentration below 1ngg−1 within the 50–120% range at relative standard deviation (RSD) as low as possible. A method to determine low level PCBs and PBDEs in milk fat based on the semi-permeable membrane dialysis/ion trap GC MS technique was developed. Validation experiments proved that the method performance was within bounds set by the currently standing UE regulations. Recovery rates calculated on the basis of labeled internal standards for majority of the studied indicator PCB congeners and PBDE congeners were close to 100% at RSD below 20%. Also, dioxin-like PCBs recovery rates were compatible with the 1883/2006 EC Regulation (80–120%, RSD below 15%). The developed method turned out to be linear within a far broader concentration range than the studied 0.0025–10pgμL−1 range entirely sufficient for analyses of PCB and PBDE in milk fat. Within that range coefficient of linear correlation (R 2) of calibration curves exceeded 0.98.

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Graphical abstract Highlights

► We have investigated the usefulness of SPM dialysis for determination of PCB/PBDE. ► The factors affecting the dialysis process were evaluated. ► The ion trap MS was optimized for determination of PCB/PBDE in milk fat. ► Described extraction/clean up method proves usefulness for the milk fat analysis.

Determination of eight fluoroquinolones in groundwater samples with ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction prior to high-performance liquid chromatography and fluorescence detection

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 748
M.M. Parrilla Vázquez, P. Parrilla Vázquez, M. Martínez Galera, M.D. Gil García
An ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of eight fluoroquinolones (marbofloxacin, norfloxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, oxolinic acid and nalidixic acid) in groundwater, using high-performance liquid chromatography with fluorescence detection (HPLC-FD). The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.4mL of methanol), which increased the extraction efficiency and reduced the equilibrium time. For the DLLME procedure, the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM] [PF6]) and methanol (MeOH) were used as extraction and disperser solvent, respectively. By comparing [C8MIM] [PF6] with 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM] [PF6]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM] [PF6]) as extraction solvents, it was observed that when using [C8MIM] [PF6] the cloudy solution was formed more readily than when using [C6MIM] [PF6] or [C4MIM] [PF6]. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, cooling in ice-water, sonication time, centrifuging time, sample pH and ionic strength, were optimised. A slight increase in the recoveries of fluoroquinolones was observed when an ice-water bath extraction step was included in the analytical procedure (85–107%) compared to those obtained without this step (83–96%). Under the optimum conditions, linearity of the method was observed over the range 10–300ngL−1 with correlation coefficient >0.9981. The proposed method has been found to have excellent sensitivity with limit of detection between 0.8 and 13ngL−1 and precision with relative standard deviation values between 4.8 and 9.4% (RSD, n =5). Good enrichment factors (122–205) and recoveries (85–107%) were obtained for the extraction of the target analytes in groundwater samples. This simple and economic method has been successfully applied to analyse real groundwater samples with satisfactory results.

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► A novel method by US-IL-DLLME-LC-FD for fluoroquinolones determination. ► Simple, rapid and efficient method for water samples. ► Advantages over conventional methods. ► Low detection limits.

A new HPLC-DAD-MS/MS method for the simultaneous determination of major compounds in the crude extract of Lychnophora salicifolia Mart. (Brazilian arnicão) leaves: Application to chemical variability evaluation

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 748
Dayana Rubio Gouvea, Fernando Meloni, Arthur de Barros Bello Ribeiro, João Luis Callegari Lopes, Norberto Peporine Lopes
Lychnophora salicifolia Mart., which occurs in the Brazilian Cerrado in the states of Bahia and Minas Gerais as well as in the southeast of the state of Goiás, is the most widely distributed and also the most polymorphic species of the genus. This plant is popularly known to have anti-inflammatory and analgesic activities. In this work, we have studied the variation in terms of polar metabolites of ninety-three Lychnophora salicifolia Mart. specimens collected from different regions of the Brazilian Cerrado. Identification of the constituents of this mixture was carried out by analysis of the UV spectra and MS data after chromatographic separation. Twenty substances were identified, including chlorogenic acid derivatives, a flavonoid C-glucoside, and other sesquiterpenes. The analytical method was validated, and the reliability and credibility of the results was ensured for the purposes of this study. The concentration range required for analysis of content variability within the analyzed group of specimens was covered with appropriate values of limits of detection and quantitation, as well as satisfactory precision and recovery. A quantitative variability was observed among specimens collected from the same location, but on average they were similar from a chemical viewpoint. In relation to the study involving specimens from different locations, there were both qualitative and quantitative differences among plants collected from different regions of Brazil. Statistical analysis revealed that there is a correlation between geographical localization and polar metabolites profile for specimens collected from different locations. This is evidence that the pattern of metabolites concentration depends on the geographical distribution of the specimens.

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Graphical abstract Highlights

Statistical analysis revealed that there is a correlation between geographical localization of Lychnophora salicifolia samples and polar metabolites profile for specimens collected from different locations.
► A new HPLC-DAD-MS method for analysis of the crude extract of L. salicifolia leaves. ► Twenty substances were identified. ► Ninety-three wild specimens were analyzed. ► A correlation between geographic isolation and decrease of the chemical similarity. ► The pattern of metabolites depends on the geographical distribution of the specimens.

Characterizing uranium oxide reference particles for isotopic abundances and uranium mass by single particle isotope dilution mass spectrometry

09 October 2012, 08:41:02
Publication year: 2012
Source:Analytica Chimica Acta, Volume 748
M. Kraiem, S. Richter, N. Erdmann, H. Kühn, M. Hedberg, Y. Aregbe
Uranium and plutonium particulate test materials are becoming increasingly important as the reliability of measurement results has to be demonstrated to regulatory bodies responsible for maintaining effective nuclear safeguards. In order to address this issue, the Institute for Reference Materials and Measurements (IRMM) in collaboration with the Institute for Transuranium Elements (ITU) has initiated a study to investigate the feasibility of preparing and characterizing a uranium particle reference material for nuclear safeguards, which is finally certified for isotopic abundances and for the uranium mass per particle. Such control particles are specifically required to evaluate responses of instruments based on mass spectrometric detection (e.g. SIMS, TIMS, LA-ICPMS) and to help ensuring the reliability and comparability of measurement results worldwide. In this paper, a methodology is described which allows quantifying the uranium mass in single micron particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS). This methodology is characterized by substantial improvements recently achieved at IRMM in terms of sensitivity and measurement accuracy in the field of uranium particle analysis by TIMS. The use of monodisperse uranium oxide particles prepared using an aerosol generation technique developed at ITU, which is capable of producing particles of well-characterized size and isotopic composition was exploited. The evidence of a straightforward correlation between the particle volume and the mass of uranium was demonstrated in this study. Experimental results have shown that the uranium mass per particle can be measured via the ID-TIMS method to a relative expanded uncertainty of about 10% (coverage factor k =2). The availability of reliable and validated methods for the characterization of uranium particles is considered to be essential for the establishment of SI-traceable measurement results. It is therefore expected that the method developed in this study is valuable for the certification of particulate materials in which the isotopic composition and the content of uranium must be accurately known.

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Graphical abstract Highlights

► A method to quantify the U mass in single micron particles by ID-TIMS was developed. ► Well-characterized monodisperse U-oxide particles produced by an aerosol generator were used. ► A linear correlation between the mass of U and the volume of particle(s) was found. ► The method developed is suitable for determining the amount of U in a particulate reference material.

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