Publicaciones

@article{RODLERRORBO2025106122,

title = {Cinnabar for Roman Ephesus: Material quality, processing and provenance},

author = {Alexandra Rodler-Rørbo and Anthony J. Baragona and Eliah J. Verbeemen and Lasse Vilien Sørensen and Berk Çakmakoğlu and Cahit Helvaci and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Frank Vanhaecke and Hilary Becker and Gilberto Artioli and Lilli Zabrana and Vinciane Debaille and Nadine Mattielli and Steven Goderis and Philippe Claeys},

url = {https://www.sciencedirect.com/science/article/pii/S0305440324001900},

doi = {https://doi.org/10.1016/j.jas.2024.106122},

issn = {0305-4403},

year  = {2025},

date = {2025-01-01},

journal = {Journal of Archaeological Science},

volume = {173},

pages = {106122},

abstract = {Ephesus was an important harbor city that flourished during the Roman period and ancient texts mention Almadén in Spain and the Cilbian fields of Ephesus as important cinnabar sources in antiquity. This work investigates whether imported cinnabar was used and whether this could be related to changes in painting activities over time. Microscopic analysis indicates a consistent preparation of cinnabar, hinting at a uniform source material quality or processing technique. However, the use of cinnabar varies among the architectural structures studied, indicating a plurality of painting techniques. A few of the analyzed cinnabar samples overlap with Turkish- and Balkan reference Pb isotope ratios; three samples from tabernas, however, deviate from this. The Hg isotope ratios reveal that cinnabar from carbonate-hosted deposits was likely used, and that processing of cinnabar included heating as suggested by ancient texts. Most notably, a correlation exists between the geochemical data and the painting technique – shifts in sourcing and cinnabar usage are potentially assignable to building chronology and/or usage. Through the lens of material provenance and processing, Ephesian cinnabar brings the organization of pigment trade into focus.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{doi:10.1021/acsagscitech.4c00613,

title = {Foliar Application of SeNPs for Rice Biofortification: a Comparative Study with Selenite and Speciation Assessment},

author = {Bruna Moreira Freire and Camila Neves Lange and Caroline Cristine Augusto and Fernanda Ribeiro Onwuatu and Gustavo Dell’Arno Principe Rodrigues and Joana Claudio Pieretti and Amedea Barozzi Seabra and Bruno Lemos Batista},

url = {https://doi.org/10.1021/acsagscitech.4c00613},

doi = {10.1021/acsagscitech.4c00613},

year  = {2024},

date = {2024-12-17},

journal = {ACS Agricultural Science & Technology},

volume = {0},

number = {0},

pages = {null},

keywords = {},

pubstate = {forthcoming},

tppubtype = {article}

}

@article{Reis2024,

title = {Platinum Deposition in the Central Nervous System: A Novel Insight into Oxaliplatin-induced Peripheral Neuropathy in Young and Old Mice},

author = {Angélica S. Reis and Jaini J. Paltian and William B. Domingues and Diogo L. R. Novo and Eduardo Bolea-Fernandez and Thibaut Van Acker and Vinicius F. Campos and Cristiane Luchese and Frank Vanhaecke and Marcia F. Mesko and Ethel A. Wilhelm},

doi = {10.1007/s12035-024-04430-y},

issn = {1559-1182},

year  = {2024},

date = {2024-09-25},

journal = {Mol Neurobiol},

publisher = {Springer Science and Business Media LLC},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{doi:10.1177/00037028241263567b,

title = {EXPRESS: Landmark Publications in Analytical Atomic Spectrometry: Fundamentals and Instrumentation Development},

author = {George C. -Y. Chan and Gary M. Hieftje and Nicoló Omenetto and Ove Axner and Arne Bengtson and Nicolas H. Bings and Michael W. Blades and Annemie Bogaerts and Mikhail A. Bolshov and José A. C. Broekaert and WingTat Chan and José M. Costa-Fernández and Stanley R. Crouch and Alessandro De Giacomo and Alessandro D’Ulivo and Carsten Engelhard and Heinz Falk and Paul B. Farnsworth and Stefan Florek and Gerardo Gamez and Igor B. Gornushkin and Detlef Günther and David W. Hahn and Wei Hang and Volker Hoffmann and Norbert Jakubowski and Vassili Karanassios and David W. Koppenaal and R. Kenneth Marcus and Reinhard Noll and John W. Olesik and Vincenzo Palleschi and Ulrich Panne and Jorge Pisonero and Steven J. Ray and Martín Resano and Richard E. Russo and Alexander Scheeline and Benjamin W. Smith and Ralph E. Sturgeon and José-Luis Todolí and Elisabetta Tognoni and Frank Vanhaecke and Michael R. Webb and James D. Winefordner and Lu Yang and Jin Yu and Zhanxia Zhang},

url = {https://doi.org/10.1177/00037028241263567},

doi = {10.1177/00037028241263567},

year  = {2024},

date = {2024-06-16},

urldate = {2024-06-16},

journal = {Applied Spectroscopy},

volume = {0},

number = {ja},

pages = {00037028241263567},

abstract = {The almost-two-centuries history of spectrochemical analysis has generated a body of literature so vast that it has become nearly intractable for experts, much less for those wishing to enter the field. Authoritative, focused reviews help to address this problem but become so granular that the overall directions of the field are lost. This broader perspective can be provided partially by general overviews but then the thinking, experimental details, theoretical underpinnings and instrumental innovations of the original work must be sacrificed. In the present compilation, this dilemma is overcome by assembling the most impactful publications in the area of analytical atomic spectrometry. Each entry was proposed by at least one current expert in the field and supported by a narrative that justifies its inclusion. The entries were then assembled into a coherent sequence and returned to contributors for a round-robin review.},

note = {PMID: 38881037},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{D3JA00420A,

title = {Boron elemental and isotopic determination via the BF diatomic molecule using high-resolution continuum source graphite furnace molecular absorption spectrometry},

author = {Maite Aramendía and André L. M. Souza and Flávio V. Nakadi and Martín Resano},

url = {http://dx.doi.org/10.1039/D3JA00420A},

doi = {10.1039/D3JA00420A},

year  = {2024},

date = {2024-01-01},

urldate = {2024-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {39},

pages = {767-779},

publisher = {The Royal Society of Chemistry},

abstract = {Boron trace determination in biological materials is needed in different fields of application. Direct B determination by means of Graphite Furnace Atomic Absorption Spectrometry (SS-GFAAS) has been used in the past for this purpose, offering good detection limits hardly achievable by other techniques. However, such methods require the use of high atomization temperatures combined with large integration times to promote B atomization, which dramatically reduces the lifetime of the instrument's graphite parts. In this work, a new perspective for B determination by means of Graphite Furnace Molecular Absorption Spectrometry (GFMAS) is proposed. B was detected as the diatomic molecule BF (boron monofluoride), deploying a gas phase reaction with CH3F as fluorinating agent. Based on this strategy, a method for the direct determination of B in two biological certified reference materials (NIST SRM 1570a spinach leaves and NIST SRM 1573a tomato leaves) has been developed, providing similar detection capabilities to the GFAAS method (LOD of 0.24 ng) but requiring much milder furnace conditions. Moreover, the appearance of memory effects, very common in GFAAS methods, is also avoided with this method. Straightforward calibration with aqueous standard solutions was also found to be possible. To this end, a mixture of W (permanent), citric acid, and Ca as chemical modifiers was found to be essential for obtaining a reproducible and sufficiently sensitive signal for boron solutions, comparable to the signals obtained for the solid samples. With this method, accurate results were obtained for the direct analysis of both certified reference materials, provided that spectral interferences from the PO molecule were properly corrected. Precision values in the range of 15% RSD, as typically reported for direct solid sampling GFAAS, were found. Finally, and as an additional advantage of the GFMAS method, a large isotopic shift in the absorbance of the 10BF and 11BF molecules can be accurately monitored at a secondary transition for the BF molecule. This offers novel analytical possibilities for the method, which are also explored in this study. In this regard, control of the B concentration was found to be critical for obtaining accurate and precise isotope ratios for this element.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{D3JA00414G,

title = {Extending the application range of Hg isotopic analysis to sub-μg L−1 levels using cold vapor generation multi-collector inductively coupled plasma-mass spectrometry with 1013 ohm Faraday cup amplifiers},

author = {Laura Suárez-Criado and Eduardo Bolea-Fernandez and Lana Abou-Zeid and Mathias Vandermeiren and Pablo Rodríguez-González and Jose Ignacio Garcia Alonso and Frank Vanhaecke},

url = {http://dx.doi.org/10.1039/D3JA00414G},

doi = {10.1039/D3JA00414G},

year  = {2024},

date = {2024-01-01},

urldate = {2024-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {39},

issue = {2},

pages = {592-600},

publisher = {The Royal Society of Chemistry},

abstract = {High-precision determination of the isotopic composition of mercury (Hg) is of paramount importance for unraveling its biogeochemical cycle and for identifying the origin of Hg in environmental compartments. Cold vapor generation multi-collector inductively coupled plasma-mass spectrometry (CVG-MC-ICP-MS) is the standard approach for such application. Cold vapor generation provides a high Hg introduction efficiency into the ICP, while chromatographic Hg isolation is not required as a result of the selective reaction between Hg2+ and SnCl2. For environmental or biota samples with low Hg concentrations, however, this approach still presents challenges and reliable measurements typically require a Hg concentration ≥1 μg L−1 in the solution analyzed. Recent improvements of MC-ICP-MS instrumentation, including the introduction of the so-called Jet interface and 1013 Ω Faraday cup amplifiers, enhance the signal-to-noise ratio. In this study, it was investigated to what extent this allows Hg isotopic analysis at lower concentration. Performance in Hg isotopic analysis was compared using two different sets of cones (standard vs. Jet), two plasma conditions (wet vs. dry) and two amplifier types (1011 Ω vs. 1013 Ω). Satisfactory accuracy and precision were achieved at a Hg concentration down to 0.1 μg L−1 in the solution measured when using Jet cones, dry plasma conditions, and the four available 1013 Ω amplifiers. The uncertainty expressed as 2SD for the δ202Hg values measured for the in-house standard solution was ±0.2‰ at 0.25 μg Hg L−1 and ± 0.3‰ at 0.1 μg Hg L−1. The method was subsequently applied to the analysis of real surface water samples contaminated with toxic metals.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{D3JA00271C,

title = {A comparison of calibration strategies for quantitative laser ablation ICP-mass spectrometry (LA-ICP-MS) analysis of fused catalyst samples},

author = {Ana Rua-Ibarz and Thibaut Van Acker and Eduardo Bolea-Fernandez and Marina Boccongelli and Frank Vanhaecke},

url = {http://dx.doi.org/10.1039/D3JA00271C},

doi = {10.1039/D3JA00271C},

year  = {2024},

date = {2024-01-01},

urldate = {2024-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {39},

issue = {3},

pages = {888-899},

publisher = {The Royal Society of Chemistry},

abstract = {In the field of petrochemistry, the quantitative determination of trace elements in catalysts is crucial for optimizing various types of processes. Catalyst poisoning, resulting from the presence of contaminants, can lead to decreased performance and efficiency, even when these are present at trace level only. Inductively coupled plasma-mass spectrometry (ICP-MS) is a powerful technique for trace elemental analysis, but its application to catalysts is challenging due to their physicochemical characteristics challenging straightforward dissolution. Laser ablation (LA) coupled to ICP-MS (LA-ICP-MS) has emerged as a valuable approach for direct analysis of solid samples. However, developing an appropriate calibration strategy for reliable quantitative LA-ICP-MS analysis of catalyst samples remains a challenge. In this work, different calibration strategies for quantitative LA-ICP-MS analysis of fused catalyst samples were evaluated. The traditional strategy relied on external calibration against certified reference materials (CRMs) combined with internal standardization and was considered the reference approach. When using this approach, the relative bias with respect to the reference value was found to be <15%. Two novel calibration strategies were introduced and compared: a so-called multi-signal calibration approach and a solution-based calibration approach. The multi-signal calibration strategy involved varying the laser repetition rate (20, 30, 40 and 50 Hz) or laser beam diameter (10, 12, 15 and 20 μm), allowing a calibration curve to be constructed by comparing the analytical signal intensity for a single solid CRM with that for the sample, thus partially overcoming the shortage of CRMs for quantitative LA-ICP-MS analysis. The solution-based calibration approach was used for quantitative multi-element analysis without the need for any solid standard and required only minor hardware modifications to accommodate the introduction of aqueous standard solutions for calibration. Various glass certified reference materials were used for method development, calibration, and validation purposes. Furthermore, two fused alumina catalyst samples (used in the context of petroleum refining processes) were successfully analyzed as a proof-of-concept application. For both the multi-signal (matrix-matched conditions) and the solution-based calibration approaches, the average relative bias between the experimentally determined and certified/reference concentrations varied between −9% and +7%.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{BOLEAFERNANDEZ2024126210,

title = {Development and initial evaluation of a combustion-based sample introduction system for direct isotopic analysis of mercury in solid samples via multi-collector ICP-mass spectrometry},

author = {Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Jorge Alves Anjos and Frank Vanhaecke},

url = {https://www.sciencedirect.com/science/article/pii/S0039914024005897},

doi = {https://doi.org/10.1016/j.talanta.2024.126210},

issn = {0039-9140},

year  = {2024},

date = {2024-01-01},

urldate = {2024-01-01},

journal = {Talanta},

volume = {276},

pages = {126210},

abstract = {High-precision isotopic analysis of mercury (Hg) using multi-collector ICP-mass spectrometry (MC-ICP-MS) is a powerful method for obtaining insight into the sources, pathways and sinks of this toxic metal. Modification of a commercially available mercury analyzer (Teledyne Leeman Labs, Hydra IIc – originally designed for quantification of Hg through sample combustion, collection of the Hg vapor on a gold amalgamator, subsequent controlled release of Hg and detection using cold vapor atomic absorption spectrometry CVAAS) enabled the system to be used for the direct high-precision Hg isotopic analysis of solid samples using MC-ICP-MS – i.e., without previous sample digestion and subsequent dilution. The changes made to the mercury analyzer did not compromise its (simultaneous) use for Hg quantification via CVAAS. The Hg vapor was mixed with a Tl-containing aerosol produced via pneumatic nebulization, creating wet plasma conditions, and enabling the use of Tl as an internal standard for correction of instrumental mass discrimination. Accurate and precise (0.10 ‰ 2SD, δ202Hg},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{FREIRE2024126417,

title = {Tracing isotopically labeled selenium nanoparticles in plants via single-particle ICP-mass spectrometry},

author = {Bruna Moreira Freire and Ana Rua-Ibarz and Flávio Venâncio Nakadi and Eduardo Bolea-Fernandez and Juan J. Barriuso-Vargas and Camila Neves Lange and Maite Aramendía and Bruno Lemos Batista and Martín Resano},

url = {https://www.sciencedirect.com/science/article/pii/S0039914024007963},

doi = {https://doi.org/10.1016/j.talanta.2024.126417},

issn = {0039-9140},

year  = {2024},

date = {2024-01-01},

journal = {Talanta},

volume = {277},

pages = {126417},

abstract = {Abstract 

Agronomic biofortification using selenium nanoparticles (SeNPs) shows potential for addressing selenium deficiency but further research on SeNPs-plants interaction is required before it can be effectively used to improve nutritional quality. In this work, single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) was used for tracing isotopically labeled SeNPs (82SeNPs) in Oryza sativa L. tissues. For this purpose, SeNPs with natural isotopic abundance and 82SeNPs were synthesized by a chemical method. The NPs characterization by transmission electron microscopy (TEM) confirmed that enriched NPs maintained the basic properties of unlabeled NPs, showing spherical shape, monodispersity, and sizes in the nano-range (82.8 ± 6.6 nm and 73.2 ± 4.4 nm for SeNPs and 82SeNPs, respectively). The use of 82SeNPs resulted in an 11-fold enhancement in the detection power for ICP-MS analysis, accompanied by an improvement in the signal-to-background ratio and a reduction of the size limits of detection from 89.9 to 39.9 nm in SP-ICP-MS analysis. This enabled 82SeNPs to be tracked in O. sativa L. plants cultivated under foliar application of 82SeNPs. Tracing studies combining SP-ICP-MS and TEM-energy-dispersive X-ray spectroscopy data confirmed the uptake of intact 82SeNPs by rice leaves, with most NPs remaining in the leaves and very few particles translocated to shoots and roots. Translocation of Se from leaves to roots and shoots was found to be lower when applied as NPs compared to selenite application. From the size distributions, as obtained by SP-ICP-MS, it can be concluded that a fraction of the 82SeNPs remained within the same size range as that of the applied NP suspension, while other fraction underwent an agglomeration process in the leaves, as confirmed by TEM images. This illustrates the potential of SP-ICP-MS analysis of isotopically enriched 82SeNPs for tracing NPs in the presence of background elements within complex plant matrices, providing important information about the uptake, accumulation, and biotransformation of SeNPs in rice plants.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{BAZO2024343305,

title = {Intensity- and time-based strategies for micro/nano-sizing via single-particle ICP-mass spectrometry: A comparative assessment using Au and SiO2 as model particles},

author = {Antonio Bazo and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Maite Aramendía and Martín Resano},

url = {https://www.sciencedirect.com/science/article/pii/S0003267024011061},

doi = {https://doi.org/10.1016/j.aca.2024.343305},

issn = {0003-2670},

year  = {2024},

date = {2024-01-01},

journal = {Analytica Chimica Acta},

volume = {1331},

pages = {343305},

abstract = {Background 

Single-particle ICP-mass spectrometry (SP-ICP-MS) is a powerful method for micro/nano-particle (MNP) sizing. Despite the outstanding evolution of the technique in the last decade, most studies still rely on traditional approaches based on (1) the use of integrated intensity as the analytical signal and (2) the calculation of the transport efficiency (TE). However, the increasing availability of MNP standards and advancements in hardware and software have unveiled new venues for MNP sizing, including TE-independent and time-based approaches. This work systematically examines these different methodologies to identify and summarize their strengths and weaknesses, thus helping to determine their preferred application areas. 

Results 

Different SP-ICP-MS methods for MNP sizing were assessed using AuNPs (20–70 nm) and SiO2MNPs (100–1000 nm). Among TE-dependent approaches, the particle frequency method was characterized by larger uncertainties than the particle size method. The results of the latter were dependent on the appropriate selection of the reference MNP, making the use of multiple reference MNPs recommended. TE-independent methods were based on external (linear and polynomial) calibrations and a relative approach. These methods exhibited the lowest uncertainties of all the strategies evaluated. External calibrations benefited from simpler calculations, but their application could be hindered by a lack of reference MNPs within the desired size range or by the need for interpolations outside the calibration range. Finally, transit time signals are directly proportional to the MNP size rather than its mass. The time-based method demonstrated adequate performance for sizing AuNPs but failed when sizing the largest SiO2MNPs (1000 nm). 

Significance and novelty 

This work provides further insights into the application of different SP-ICP-MS methodologies for MNP sizing. Both TE-independent approaches and the monitoring of the transit time as the analytical signal are underused strategies; in this context, a Python script was developed for accurate transit time measurement. After 20 years of development, a quantitative comparison of the different methodologies, including the most novel approaches, is deemed necessary for further growth on solid theoretical ground.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{D4JA90052A,

title = {Atomic spectrometry update: review of advances in the analysis of metals, chemicals and materials},

author = {Eduardo Bolea-Fernandez and Robert Clough and Andy Fisher and Bridget Gibson and Ben Russell},

url = {http://dx.doi.org/10.1039/D4JA90052A},

doi = {10.1039/D4JA90052A},

year  = {2024},

date = {2024-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {39},

issue = {11},

pages = {2617-2693},

publisher = {The Royal Society of Chemistry},

abstract = {This update covers the literature published between approximately June 2023 and April 2024 and is the latest part of a series of annual reviews. It is designed to provide the reader with an overview of the current state of the art with respect to the atomic spectrometric analysis of various metals, chemicals and materials. Data processing appears to be the hottest topic in many of the areas. This is especially true for LIBS and (TOF)-SIMS, where huge amounts of data can be acquired. Methods have been used to decrease the dimensions of the data whilst still retaining the most important information. This can then be input into a machine-learning algorithm so that the provenance of a sample, the sample type, or, in the case of TOF-SIMS data, a clear characterisation of the surface of the sample can be obtained while using less computing power and less processing time. Although these algorithms have been used for some years, their use is expanding into new areas. Another development is the combination of complementary techniques on the same instrument platform. This enables data from the two techniques to be obtained simultaneously and from the same spot on the sample. With regard to the different analytical techniques used, LIBS is continuing to increase in popularity, bolstering its reputation as being the rising superstar of the analytical world.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{DEJONGHE2024112013,

title = {An evaluation of the analytical and biological robustness of a method for quantifying iron in individual red blood cells via single-cell tandem ICP-mass spectrometry},

author = {Rinus Dejonghe and Eduardo Bolea-Fernandez and Ana Lores-Padin and Thibaut Van Acker and Ana Rua-Ibarz and Olivier De Wever and Frank Vanhaecke},

url = {https://www.sciencedirect.com/science/article/pii/S0026265X24021258},

doi = {https://doi.org/10.1016/j.microc.2024.112013},

issn = {0026-265X},

year  = {2024},

date = {2024-01-01},

journal = {Microchemical Journal},

volume = {207},

pages = {112013},

abstract = {This work evaluated the analytical and biological robustness of iron (Fe) determination in individual red blood cells (RBCs) via single-cell ICP-MS (SC-ICP-MS). RBCs were separated from other whole blood constituents using Ficoll-Paque™ density gradient centrifugation. While fixation with paraformaldehyde (PFA) led to RBC lysis, the use of glutaraldehyde (GA) left the RBCs intact and permitted storage of RBC suspensions in ultra-pure water for up to 16 months at 4 °C. GA-fixation also rendered the RBCs sufficiently robust to maintain integrity during their introduction into the ICP by means of nebulization of dilute suspensions. Obtaining quantitative data on a cell-per-cell basis required determination of the transport efficiency using the particle size method and external calibration against aqueous Fe standard solutions. The average Fe content per RBC obtained using SC-ICP-MS (103 fg/cell) agreed well with the value obtained using solution-based ICP-MS obtained after cell pellet digestion and with values obtained from literature. Variation of the cell number density in the suspensions analyzed between 1.5 × 105 and 6.0 × 105 cells per mL did not affect the result. Identical results from one-week interval blood drawings from healthy individuals demonstrate biological consistency. Compared to bulk analysis, the SC-ICP-MS approach offers the added value of providing information on the cell-to-cell heterogeneity in Fe content.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Laser Ablation for Nondestructive Sampling of Microplastics in Single-Particle ICP-Mass Spectrometry},

author = {Thibaut Van Acker and Ana Rua-Ibarz and Frank Vanhaecke and Eduardo Bolea-Fernandez},

url = {https://doi.org/10.1021/acs.analchem.3c04473},

doi = {10.1021/acs.analchem.3c04473},

year  = {2023},

date = {2023-12-05},

urldate = {2023-12-05},

journal = {Anal. Chem.},

volume = {95},

issue = {50},

pages = {18579-18586},

abstract = {In this work, laser ablation (LA) was characterized as a method for sampling and introducing microplastic particles (MPs) into an inductively coupled plasma (ICP) for subsequent 13C+ monitoring using an ICP-mass spectrometer operated in single-event mode. MPs of different types (PS, PMMA, and PVC) and sizes (2–20 μm) were introduced intactly. The laser energy density did not affect the particle sampling across a wide range (0.25–6.00 J cm–2). Single-shot analysis separated clustered MPs (2–7 MPs per cluster) during the LA and particle transport processes, allowing the temporally resolved analysis of the individual constituting MPs. Line scanning showed superior performance when using a small laser beam diameter combined with a high repetition rate. The 13C+ signal intensity correlated linearly (R2 >0.9945) with the absolute C mass in a 2–10 μm size range, while the use of He in the collision-reaction cell (CRC) allowed extension of the linear range to 20 μm. The LA approach generated narrower 13C+ signal distributions than the traditional solution-based approach (dry versus wet plasma conditions) and proved successful for the analysis of a mixed suspension (containing four sizes of PS MPs in a 2–5 μm size range) and for sampling MPs from PVDF and glass microfiber filters, with the latter offering a lower background.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Serum Mg Isotopic Composition Reveals That Mg Dyshomeostasis Remains in Type 1 Diabetes despite the Resolution of Hypomagnesemia},

author = {Kaj Vaughan Sullivan and Yasmina Assantuh and Rosa Grigoryan and Marta Costas-Rodríguez and Eduardo Bolea-Fernandez and Bruno Lapauw and Steven Van Laecke and Frank Vanhaecke},

url = {https://doi.org/10.3390/ijms242115683},

doi = {10.3390/ijms242115683},

year  = {2023},

date = {2023-10-27},

urldate = {2023-10-27},

journal = {Int. J. Mol. Sci.},

volume = {24},

issue = {21},

pages = {15683},

abstract = {Hypomagnesemia was historically prevalent in individuals with type 1 diabetes mellitus (T1DM), but contemporary results indicate an incidence comparable to that in the general population, likely due to improved treatment in recent decades, resulting in better glycemic control. However, a recent study found a significant difference between the serum Mg isotopic composition of T1DM individuals and controls, indicating that disruptions to Mg homeostasis persist. Significant deviations were also found in samples taken one year apart. To investigate whether the temporal variability in serum Mg isotopic composition is linked to the transient impact of administered insulin, Mg isotope ratios were determined in serum from 15 T1DM individuals before and one hour after insulin injection/meal consumption using multi-collector inductively coupled plasma-mass spectrometry. Consistent with results of the previous study, significant difference in the serum Mg isotopic composition was found between T1DM individuals and 10 sex-matched controls. However, the average difference between pre- and post-insulin injection/meal T1DM samples of 0.05 ± 0.13‰ (1SD) was not significant. No difference was observed for controls before (−0.12 ± 0.16‰) and after the meal (−0.10 ± 0.13‰) either, suggesting a lack of a postprandial Mg isotopic response within one hour of food consumption, and that the timing of the most recent meal may not require controlling for when determining serum Mg isotopic composition.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Isotope Dilution Analysis for Particle Mass Determination Using Single-Particle Inductively Coupled Plasma Time-of-Flight Mass Spectrometry: Application to Size Determination of Silver Nanoparticles},

author = {Maite Aramendía and Diego Leite and Javier Resano and Martín Resano and Kharmen Billimoria and Heidi Goenaga-Infante},

doi = {10.3390/nano13172392},

year  = {2023},

date = {2023-08-22},

urldate = {2023-08-22},

journal = {Nanomaterials},

volume = {13},

issue = {17},

pages = {2392},

abstract = {This paper describes methodology based on the application of isotope dilution (ID) in

single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-ToFMS) mode

for the mass determination (and sizing) of silver nanoparticles (AgNPs). For this purpose, and

considering that the analytical signal in spICP-MS shows a transient nature, an isotope dilution

equation used for online work was adapted and used for the mass determination of individual NPs.

The method proposed measures NP isotope ratios in a particle-to-particle approach, which allows for

the characterization of NP mass (and size) distributions and not only the mean size of the distribution.

For the best results to be obtained, our method development (undertaken through the analysis of

the reference material NIST RM 8017) included the optimization of the working conditions for the

best precision and accuracy in isotope ratios of individual NPs, which had been only reported to

date with multicollector instruments. It is shown that the precision of the measurement of these

ratios is limited by the magnitude of the signals obtained for each NP in the mass analyzer (counting

statistics). However, the uncertainty obtained for the sizing of NPs in this approach can be improved

by careful method optimization, where the most important parameters are shown to be the selection

of the spike isotopic composition and concentration. Although only AgNPs were targeted in this

study, the method presented, with the corresponding adaptations, could be applied to NPs of any

other composition that include an element with different naturally available isotopes.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Inductively coupled plasma mass spectrometry},

author = {Thibaut Van Acker and Sarah Theiner and Eduardo Bolea-Fernandez and Frank Vanhaecke and Gunda Koellensperger},

doi = {https://doi.org/10.1038/s43586-023-00235-w},

year  = {2023},

date = {2023-07-06},

journal = {Nature Reviews Methods Primers},

volume = {3},

pages = {52},

abstract = {Inductively coupled plasma mass spectrometry (ICP-MS) combines plasma chemistry, which produces singly charged elemental ions, with mass spectrometric detection. Unlike other mass spectrometry ionization sources, the ICP can efficiently handle liquid, solid and gaseous samples. Nuclides of metals, metalloids and some non-metals — such as sulfur, phosphorus and halogens — can be ionized, with an ionization degree that depends on the intrinsic properties of the element and sample matrix. As a stand-alone technique, ICP-MS excels in (ultra-)trace multi-elemental analysis and isotopic analysis. Combined with chromatographic separations, molecules are assessed as elemental species, whereas laser ablation-ICP-MS enables direct sampling from solid surfaces, either in the imaging modality or for bulk analysis. Scanning-type mass analysers, such as quadrupole-based mass spectrometers and sector field mass spectrometers, dominate the field. Time-of-flight ICP mass spectrometers are considered the go-to instruments for multi-elemental analysis of microscale and nanoscale particles and single cells as discrete entities in a time-resolved manner. This Primer covers the major analytical applications of ICP-MS — multi-element, single-particle, single-cell, laser ablation, speciation and isotopic analysis — and outlines the underlying measurement strategies, challenges and example applications.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{D2JA00267A,

title = {Cu fractionation, isotopic analysis, and data processing via machine learning: new approaches for the diagnosis and follow up of Wilson's disease via ICP-MS},

author = {M. Carmen García-Poyo and Sylvain Bérail and Anne Laure Ronzani and Luis Rello and Elena García-González and Flávio V. Nakadi and Maite Aramendía and Javier Resano and Martín Resano and Christophe Pécheyran},

url = {http://dx.doi.org/10.1039/D2JA00267A},

doi = {10.1039/D2JA00267A},

year  = {2023},

date = {2023-01-01},

urldate = {2023-01-01},

journal = {J. Anal. At. Spectrom.},

volume = {38},

issue = {1},

pages = {229-242},

publisher = {The Royal Society of Chemistry},

abstract = {Information about Cu fractionation and Cu isotopic composition can be paramount when investigating Wilson's disease (WD). This information can provide a better understanding of the metabolism of Cu. Most importantly, it may provide an easy way to diagnose and to follow the evolution of WD patients. For such purposes, protocols for Cu determination and Cu isotopic analysis via inductively coupled plasma mass spectrometry were investigated in this work, both in bulk serum and in the exchangeable copper (CuEXC) fractions. The CuEXC protocol provided satisfactory recovery values. Also, no significant mass fractionation during the whole analytical procedure (CuEXC production and/or Cu isolation) was detected. Analyses were carried out in controls (healthy persons), newborns, patients with hepatic disorders, and WD patients. While the results for Cu isotopic analysis are relevant (e.g., δ65Cu values were lower for both WD patients under chelating treatment and patients with hepatic problems in comparison with those values obtained for WD patients under Zn treatments, controls, and newborns) to comprehend Cu metabolism and to follow up the disease, the parameter that can help to better discern between WD patients and the rest of the patients tested (non-WD) was found to be the REC (relative exchangeable Cu). In this study, all the WD patients showed a REC higher than 17%, while the rest showed lower values. However, since establishing a universal threshold is complicated, machine learning was investigated to produce a model that can differentiate between WD and non-WD samples with excellent results (100% accuracy, albeit for a limited sample set). Most importantly, unlike other ML approaches, our model can also provide an uncertainty metric to indicate the reliability of the prediction, overall opening new ways to diagnose WD.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nano13121838,

title = {An Approach Based on an Increased Bandpass for Enabling the Use of Internal Standards in Single Particle ICP-MS: Application to AuNPs Characterization},

author = {Antonio Bazo and Maite Aramendía and Flávio V. Nakadi and Martín Resano},

url = {https://www.mdpi.com/2079-4991/13/12/1838},

doi = {10.3390/nano13121838},

issn = {2079-4991},

year  = {2023},

date = {2023-01-01},

urldate = {2023-01-01},

journal = {Nanomaterials},

volume = {13},

number = {12},

abstract = {This paper proposes a novel approach to implement an internal standard (IS) correction in single particle inductively coupled plasma mass spectrometry (SP ICP-MS), as exemplified for the characterization of Au nanoparticles (NPs) in complex matrices. This approach is based on the use of the mass spectrometer (quadrupole) in bandpass mode, enhancing the sensitivity for the monitoring of AuNPs while also allowing for the detection of PtNPs in the same measurement run, such that they can serve as an internal standard. The performance of the method developed was proved for three different matrices: pure water, a 5 g L−1 NaCl water solution, and another water solution containing 2.5% (m/v) tetramethylammonium hydroxide (TMAH)/0.1% Triton X-100. It was observed that matrix-effects impacted both the sensitivity of the NPs and their transport efficiencies. To circumvent this problem, two methods were used to determine the TE: the particle size method for sizing and the dynamic mass flow method for the determination of the particle number concentration (PNC). This fact, together with the use of the IS, enabled us to attain accurate results in all cases, both for sizing and for the PNC determination. Additionally, the use of the bandpass mode provides additional flexibility for this characterization, as it is possible to easily tune the sensitivity achieved for each NP type to ensure that their distributions are sufficiently resolved.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{BERDECKA2023101991,

title = {Photothermal nanofibers enable macromolecule delivery in unstimulated human T cells},

author = {Dominika Berdecka and Manon Minsart and Tao Lu and Deep Punj and Riet De Rycke and Mina Nikolić and Eduardo Bolea-Fernandez and Frank Vanhaecke and Ranhua Xiong and Stefaan C. De Smedt and Peter Dubruel and Winnok H. De Vos and Kevin Braeckmans},

url = {https://www.sciencedirect.com/science/article/pii/S2352940723002573},

doi = {https://doi.org/10.1016/j.apmt.2023.101991},

issn = {2352-9407},

year  = {2023},

date = {2023-01-01},

journal = {Applied Materials Today},

volume = {35},

pages = {101991},

abstract = {Cell therapies such as adoptive T cell transfer require ex vivo modification of cells with exogenous cargo to modulate their phenotype (e.g., to express a synthetic antigen receptor) for optimal therapeutic efficacy upon reinfusion in a patient. Several studies have shown superior anti-tumor activity of minimally differentiated T cell subsets over their activated counterparts. Therefore, developing techniques for safe and efficient manipulation of these quiescent cells is important for both clinical applications and fundamental studies of T cell biology. Photoporation with photothermal electrospun nanofibers (PEN) is an efficient and minimally perturbing non-viral intracellular delivery technique for activated and expanded T cells. However, the technique has not yet been applied to unstimulated T cells. Here, we investigated the potential of PEN photoporation for delivery of macromolecules into these cells. First, we confirmed with inductively coupled plasma tandem mass spectrometry that there was no significant iron release from fibers after laser activation of PEN substrates for laser fluences up to 0.36 J/cm². Next, we demonstrated successful intracellular delivery of 150 kDa FITC-dextran as model macromolecule in resting and pre-activated lymphocytes with 55–60 % delivery efficiency. By analyzing metabolic activity, activation surface marker presentation and extracellular cytokine release, we found that PEN treatment had no effect on cell proliferation and limited impact on T cell activation propensity for all tested irradiation energies. Thus, our findings show that PEN photoporation holds promise as a safe and efficient delivery strategy, paving the way for its use in genetic modification of minimally differentiated T cells.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{D3NR00435J,

title = {Results of an interlaboratory comparison for characterization of Pt nanoparticles using single-particle ICP-TOFMS},

author = {Lyndsey Hendriks and Robert Brünjes and Sara Taskula and Jovana Kocic and Bodo Hattendorf and Garret Bland and Gregory Lowry and Eduardo Bolea-Fernandez and Frank Vanhaecke and Jingjing Wang and Mohammed Baalousha and Marcus Au and Björn Meermann and Timothy Ronald Holbrook and Stephan Wagner and Stasia Harycki and Alexander Gundlach-Graham and Frank Kammer},

url = {http://dx.doi.org/10.1039/D3NR00435J},

doi = {10.1039/D3NR00435J},

year  = {2023},

date = {2023-01-01},

journal = {Nanoscale},

volume = {15},

issue = {26},

pages = {11268-11279},

publisher = {The Royal Society of Chemistry},

abstract = {This study describes an interlaboratory comparison (ILC) among nine (9) laboratories to evaluate and validate the standard operation procedure (SOP) for single-particle (sp) ICP-TOFMS developed within the context of the Horizon 2020 project ACEnano. The ILC was based on the characterization of two different Pt nanoparticle (NP) suspensions in terms of particle mass, particle number concentration, and isotopic composition. The two Pt NP suspensions were measured using icpTOF instruments (TOFWERK AG, Switzerland). Two Pt NP samples were characterized and mass equivalent spherical sizes (MESSs) of 40.4 ± 7 nm and 58.8 ± 8 nm were obtained, respectively. MESSs showed <16% relative standard deviation (RSD) among all participating labs and <4% RSD after exclusion of the two outliers. A good agreement was achieved between the different participating laboratories regarding particle mass, but the particle number concentration results were more scattered, with <53% RSD among all laboratories, which is consistent with results from previous ILC studies conducted using ICP-MS instrumentation equipped with a sequential mass spectrometer. Additionally, the capabilities of sp-ICP-TOFMS to determine masses on a particle basis are discussed with respect to the potential for particle density determination. Finally, because quasi-simultaneous multi-isotope and multi-element determinations are a strength of ICP-TOFMS instrumentation, the precision and trueness of isotope ratio determinations were assessed. The average of 1000 measured particles yielded a precision of below ±1% for intensity ratios of the most abundant Pt isotopes, i.e.194Pt and 195Pt, while the accuracy of isotope ratios with the lower abundant isotopes was limited by counting statistics.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}