2024
Journal Articles
Aramendía, Maite; Souza, André L. M.; Nakadi, Flávio V.; Resano, Martín
En: J. Anal. At. Spectrom., vol. 39, pp. 767-779, 2024.
@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}
}
2023
Journal Articles
Acker, Thibaut Van; Rua-Ibarz, Ana; Vanhaecke, Frank; Bolea-Fernandez, Eduardo
Laser Ablation for Nondestructive Sampling of Microplastics in Single-Particle ICP-Mass Spectrometry Journal Article
En: Anal. Chem., vol. 95, iss. 50, pp. 18579-18586, 2023.
@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},
doi = {https://doi.org/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}
}
Sullivan, Kaj Vaughan; Assantuh, Yasmina; Grigoryan, Rosa; Costas-Rodríguez, Marta; Bolea-Fernandez, Eduardo; Lapauw, Bruno; Laecke, Steven Van; Vanhaecke, Frank
Serum Mg Isotopic Composition Reveals That Mg Dyshomeostasis Remains in Type 1 Diabetes despite the Resolution of Hypomagnesemia Journal Article
En: Int. J. Mol. Sci., vol. 24, iss. 21, pp. 15683, 2023.
@article{pmid37958667,
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},
doi = {10.3390/ijms242115683},
year = {2023},
date = {2023-10-01},
urldate = {2023-10-01},
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}
}
Aramendía, Maite; Leite, Diego; Resano, Javier; Resano, Martín; Billimoria, Kharmen; Goenaga-Infante, Heidi
En: Nanomaterials, vol. 13, iss. 17, pp. 2392, 2023.
@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}
}
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.
Acker, Thibaut Van; Theiner, Sarah; Bolea-Fernandez, Eduardo; Vanhaecke, Frank; Koellensperger, Gunda
Inductively coupled plasma mass spectrometry Journal Article
En: Nature Reviews Methods Primers, vol. 3, pp. 52, 2023.
@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}
}
García-Poyo, M. Carmen; Bérail, Sylvain; Ronzani, Anne Laure; Rello, Luis; García-González, Elena; Nakadi, Flávio V.; Aramendía, Maite; Resano, Javier; Resano, Martín; Pécheyran, Christophe
En: J. Anal. At. Spectrom., vol. 38, iss. 1, pp. 229-242, 2023.
@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},
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}
}
Bazo, Antonio; Aramendía, Maite; Nakadi, Flávio V.; Resano, Martín
En: Nanomaterials, vol. 13, no. 12, 2023, ISSN: 2079-4991.
@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},
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}
}
Berdecka, Dominika; Minsart, Manon; Lu, Tao; Punj, Deep; Rycke, Riet De; Nikolić, Mina; Bolea-Fernandez, Eduardo; Vanhaecke, Frank; Xiong, Ranhua; Smedt, Stefaan C. De; Dubruel, Peter; Vos, Winnok H. De; Braeckmans, Kevin
Photothermal nanofibers enable macromolecule delivery in unstimulated human T cells Journal Article
En: Applied Materials Today, vol. 35, pp. 101991, 2023, ISSN: 2352-9407.
@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}
}
Hendriks, Lyndsey; Brünjes, Robert; Taskula, Sara; Kocic, Jovana; Hattendorf, Bodo; Bland, Garret; Lowry, Gregory; Bolea-Fernandez, Eduardo; Vanhaecke, Frank; Wang, Jingjing; Baalousha, Mohammed; Au, Marcus; Meermann, Björn; Holbrook, Timothy Ronald; Wagner, Stephan; Harycki, Stasia; Gundlach-Graham, Alexander; Kammer, Frank
Results of an interlaboratory comparison for characterization of Pt nanoparticles using single-particle ICP-TOFMS Journal Article
En: Nanoscale, vol. 15, iss. 26, pp. 11268-11279, 2023.
@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}
}
2022
Journal Articles
Aramendía, Maite; García-Mesa, Juan Carlos; Alonso, Elisa Vereda; Garde, Raúl; Bazo, Antonio; Resano, Javier; Resano, Martín
En: Analytica Chimica Acta, vol. 1205, pp. 339738, 2022, ISSN: 0003-2670.
@article{ARAMENDIA2022339738,
title = {A novel approach for adapting the standard addition method to single particle-ICP-MS for the accurate determination of NP size and number concentration in complex matrices},
author = {Maite Aramendía and Juan Carlos García-Mesa and Elisa Vereda Alonso and Raúl Garde and Antonio Bazo and Javier Resano and Martín Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0003267022003099},
doi = {https://doi.org/10.1016/j.aca.2022.339738},
issn = {0003-2670},
year = {2022},
date = {2022-01-01},
journal = {Analytica Chimica Acta},
volume = {1205},
pages = {339738},
abstract = {This paper presents a novel approach, based on the standard addition method, for overcoming the matrix effects that often hamper the accurate characterization of nanoparticles (NPs) in complex samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). In this approach, calibration of the particle size is performed by two different methods: (i) by spiking a suspension of NPs standards of known size containing the analyte, or (ii) by spiking the sample with ionic standards; either way, the measured sensitivity is used in combination with the transport efficiency (TE) for sizing the NPs. Moreover, such transport efficiency can be readily obtained from the data obtained via both calibration methods mentioned above, so that the particle number concentration can also be determined. The addition of both ionic and NP standards can be performed on-line, by using a T-piece with two inlet lines of different dimensions. The smaller of the two is used for the standards, thus ensuring a constant and minimal sample dilution. As a result of the spiking of the samples, mixed histograms including the signal of the sample and that of the standards are obtained. However, the use of signal deconvolution approaches permits to extract the information, even in cases of signal populations overlapping. For proofing the concept, characterization of a 50 nm AuNPs suspension prepared in three different media (i.e., deionized water, 5% ethanol, and 2.5% tetramethyl ammonium hydroxide-TMAH) was carried out. Accurate results were obtained in all cases, in spite of the matrix effects detected in some media. Overall, the approach proposed offers flexibility, so it can be adapted to different situations, but it might be specially indicated for samples for which the matrix is not fully known and/or dilution is not possible/recommended.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Resano, M.; Aramendía, M.; García-Ruiz, E.; Bazo, A.; Bolea-Fernandez, E.; Vanhaecke, F.
Living in a transient world: ICP-MS reinvented via time-resolved analysis for monitoring single events Journal Article
En: Chem. Sci., vol. 13, iss. 16, pp. 4436-4473, 2022.
@article{D1SC05452J,
title = {Living in a transient world: ICP-MS reinvented via time-resolved analysis for monitoring single events},
author = {M. Resano and M. Aramendía and E. García-Ruiz and A. Bazo and E. Bolea-Fernandez and F. Vanhaecke},
url = {http://dx.doi.org/10.1039/D1SC05452J},
doi = {10.1039/D1SC05452J},
year = {2022},
date = {2022-01-01},
journal = {Chem. Sci.},
volume = {13},
issue = {16},
pages = {4436-4473},
publisher = {The Royal Society of Chemistry},
abstract = {After 40 years of development, inductively coupled plasma-mass spectrometry (ICP-MS) can hardly be considered as a novel technique anymore. ICP-MS has become the reference when it comes to multi-element bulk analysis at (ultra)trace levels, as well as to isotope ratio determination for metal(loid)s. However, over the last decade, this technique has managed to uncover an entirely new application field, providing information in a variety of contexts related to the individual analysis of single entities (e.g., nanoparticles, cells, or micro/nanoplastics), thus addressing new societal challenges. And this profound expansion of its application range becomes even more remarkable when considering that it has been made possible in an a priori simple way: by providing faster data acquisition and developing the corresponding theoretical substrate to relate the time-resolved signals thus obtained with the elemental composition of the target entities. This review presents the underlying concepts behind single event-ICP-MS, which are needed to fully understand its potential, highlighting key areas of application (e.g., single particle-ICP-MS or single cell-ICP-MS) as well as of future development (e.g., micro/nanoplastics).},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Navarro-Bielsa, Alba; Abadías-Granado, Isabel; Morales-Callaghan, Ana María; Suso-Estívalez, Catalina; Povar-Echeverría, Marina; Rello, Luis; Gilaberte, Yolanda
Experience with Cutaneous Manifestations in COVID-19 Patients during the Pandemic Journal Article
En: J Clin Med, vol. 11, no. 3, 2022, ISSN: 2077-0383.
@article{pmid35160051,
title = {Experience with Cutaneous Manifestations in COVID-19 Patients during the Pandemic},
author = {Alba Navarro-Bielsa and Isabel Abadías-Granado and Ana María Morales-Callaghan and Catalina Suso-Estívalez and Marina Povar-Echeverría and Luis Rello and Yolanda Gilaberte},
doi = {10.3390/jcm11030600},
issn = {2077-0383},
year = {2022},
date = {2022-01-01},
journal = {J Clin Med},
volume = {11},
number = {3},
abstract = {After the beginning of the SARS-CoV-2 pandemic, our dermatology department created a multidisciplinary unit to manage patients with cutaneous manifestations associated with COVID-19. With the objective of identifying skin lesions in patients with suspected COVID-19 and evaluating possible associations with systemic involvement, other infectious agents and coagulation disorders, we carried out a prospective observational study that included all patients that attended our COVID-19 dermatology clinic with a multidisciplinary protocol. A total of 63 patients (mean 34.6 years) were enrolled between May 2020 and February 2021. Overall, 27 patients (42.9%) had a positive COVID-19 test, and 74.6% had COVID-19 clinical signs. The most common skin lesion was maculopapular rash (36.5%), predominantly seen in male (54.2%) and older patients (42 vs. 30 years), followed by chilblain-like lesions (20.6%) in younger patients (13.9 vs. 20.9 years) who were predominantly barefoot at home (69.2%); these patients exhibited a tendency towards a negative COVID-19 test. A total of 12 patients (19.1%) had positive serology for herpesvirus 6 (IgM or IgG). We conclude that the COVID-19-associated skin lesions we observed were similar to those previously described. Questions as to the underlying mechanisms remain. Interferon, possibly aided by cold exposure, may cause perniosis-like lesions. Other cutaneous manifestations were similar to those caused by other viruses, suggesting that SARS-CoV-2 may reactivate or facilitate other viral infections.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Bazo, Antonio; Garde, Raúl; Garcia-Ruiz, Esperanza; Aramendía, Maite; Nakadi, Flávio V.; Resano, Martín
En: J. Anal. At. Spectrom., vol. 37, iss. 12, pp. 2517-2528, 2022.
@article{D2JA00245K,
title = {High-resolution continuum source graphite furnace molecular absorption spectrometry for the monitoring of Sr isotopes via SrF formation: a case study},
author = {Antonio Bazo and Raúl Garde and Esperanza Garcia-Ruiz and Maite Aramendía and Flávio V. Nakadi and Martín Resano},
url = {http://dx.doi.org/10.1039/D2JA00245K},
doi = {10.1039/D2JA00245K},
year = {2022},
date = {2022-01-01},
urldate = {2022-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {37},
issue = {12},
pages = {2517-2528},
publisher = {The Royal Society of Chemistry},
abstract = {High-resolution continuum source graphite furnace molecular absorption spectrometry (HR CS GFMAS) can provide isotopic information under certain conditions, thus broadening its field of application. However, to date, only elements with two major stable isotopes have been monitored via this technique. In this work, the possibilities of HR CS GFMAS to determine isotope ratios of elements with more than two stable isotopes are evaluated for the first time. For this purpose, Sr was chosen as the analyte and SrF as the target species, so four different signals corresponding to four stable Sr isotopes (88Sr, 87Sr, 86Sr and 84Sr) should be distinguished. Nevertheless, due to the number of strontium isotopes, the shape of the peaks, and the resolution that the instrument exhibits in the spectral window, isotopic signals overlap, thus leading to potentially biased results. To circumvent this issue, a deconvolution protocol, consisting of measuring and correcting for the contribution of each isotope on the signals of the rest, was developed. These contributions were calculated as the signal ratio between the absorbance of the monoisotopic profile at the wavelengths where the maxima of other isotopes are expected and at its own maximum. Therefore, the interference can be simply subtracted from the net signal registered for the interfered isotope. The performance of this method was demonstrated for both naturally abundant and isotope-enriched Sr standards, paving the way for future applications in this field. Analysis of a real sample (tap water) spiked with a 84Sr solution is also demonstrated.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
2021
Journal Articles
Infante, Heidi Goenaga; Chalmers, John; Dent, Geoffrey; Todoli, Jose Luis; Collingwood, Joanna; Telling, Neil; Resano, Martin; Limbeck, Andreas; Schoenberger, Torsten; Hibbert, D. Brynn; LeGresley, Adam; Adams, Kristie; Craston, Derek
Glossary of methods and terms used in analytical spectroscopy (IUPAC Recommendations 2019) Journal Article
En: Pure and Applied Chemistry, vol. 93, iss. 6, pp. 647-776, 2021.
@article{nokey,
title = {Glossary of methods and terms used in analytical spectroscopy (IUPAC Recommendations 2019)},
author = {Heidi {Goenaga Infante} and John Chalmers and Geoffrey Dent and Jose Luis Todoli and Joanna Collingwood and Neil Telling and Martin Resano and Andreas Limbeck and Torsten Schoenberger and D. Brynn Hibbert and Adam LeGresley and Kristie Adams and Derek Craston},
url = {https://www.degruyter.com/document/doi/10.1515/pac-2019-0203/html},
doi = {10.1515/pac-2019-0203},
year = {2021},
date = {2021-07-14},
urldate = {2021-07-14},
journal = {Pure and Applied Chemistry},
volume = {93},
issue = {6},
pages = {647-776},
abstract = {Recommendations are given concerning the terminology of concepts and methods used in spectroscopy in analytical chemistry, covering nuclear magnetic resonance spectroscopy, atomic spectroscopy, and vibrational spectroscopy.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Martínez-Morillo, Eduardo; García-García, María; Concha, María Angeles Luengo; Varas, Luis Rello
Evaluation of a new equation for estimating low-density lipoprotein cholesterol through the comparison with various recommended methods Journal Article
En: Biochem Med (Zagreb), vol. 31, no. 1, pp. 010701, 2021, ISSN: 1846-7482.
@article{pmid33380888,
title = {Evaluation of a new equation for estimating low-density lipoprotein cholesterol through the comparison with various recommended methods},
author = {Eduardo Martínez-Morillo and María García-García and María Angeles Luengo Concha and Luis Rello Varas},
doi = {10.11613/BM.2021.010701},
issn = {1846-7482},
year = {2021},
date = {2021-02-01},
journal = {Biochem Med (Zagreb)},
volume = {31},
number = {1},
pages = {010701},
abstract = {INTRODUCTION: The accurate estimation of low-density lipoprotein cholesterol (LDL) is crucial for management of patients at risk of cardiovascular events due to dyslipidemia. The LDL is typically calculated using the Friedewald equation and/or direct homogeneous assays. However, both methods have their own limitations, so other equations have been proposed, including a new equation developed by Sampson. The aim of this study was to evaluate Sampson equation by comparing with the Friedewald and Martin-Hopkins equations, and with a direct LDL method.
MATERIALS AND METHODS: Results of standard lipid profile (total cholesterol (CHOL), high-density lipoprotein cholesterol (HDL) and triglycerides (TG)) were obtained from two anonymized data sets collected at two laboratories, using assays from different manufacturers (Beckman Coulter and Roche Diagnostics). The second data set also included LDL results from a direct assay (Roche Diagnostics). Passing-Bablok and Bland-Altman analysis for method comparison was performed.
RESULTS: A total of 64,345 and 37,783 results for CHOL, HDL and TG were used, including 3116 results from the direct LDL assay. The Sampson and Friedewald equations provided similar LDL results (difference ≤ 0.06 mmol/L, on average) at TG ≤ 2.0 mmol/L. At TG between 2.0 and 4.5 mmol/L, the Sampson-calculated LDL showed a constant bias (- 0.18 mmol/L) when compared with the Martin-Hopkins equation. Similarly, at TG between 4.5 and 9.0 mmol/L, the Sampson equation showed a negative bias when compared with the direct assay, which was proportional (- 16%) to the LDL concentration.
CONCLUSIONS: The Sampson equation may represent a cost-efficient alternative for calculating LDL in clinical laboratories.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
MATERIALS AND METHODS: Results of standard lipid profile (total cholesterol (CHOL), high-density lipoprotein cholesterol (HDL) and triglycerides (TG)) were obtained from two anonymized data sets collected at two laboratories, using assays from different manufacturers (Beckman Coulter and Roche Diagnostics). The second data set also included LDL results from a direct assay (Roche Diagnostics). Passing-Bablok and Bland-Altman analysis for method comparison was performed.
RESULTS: A total of 64,345 and 37,783 results for CHOL, HDL and TG were used, including 3116 results from the direct LDL assay. The Sampson and Friedewald equations provided similar LDL results (difference ≤ 0.06 mmol/L, on average) at TG ≤ 2.0 mmol/L. At TG between 2.0 and 4.5 mmol/L, the Sampson-calculated LDL showed a constant bias (- 0.18 mmol/L) when compared with the Martin-Hopkins equation. Similarly, at TG between 4.5 and 9.0 mmol/L, the Sampson equation showed a negative bias when compared with the direct assay, which was proportional (- 16%) to the LDL concentration.
CONCLUSIONS: The Sampson equation may represent a cost-efficient alternative for calculating LDL in clinical laboratories.
Nakadi, Flávio V.; García-Poyo, M. Carmen; Pécheyran, Christophe; Resano, Martín
En: J. Anal. At. Spectrom., vol. 36, iss. 11, pp. 2370-2382, 2021.
@article{D1JA00233C,
title = {Time-absorbance profile ratio background correction: introducing TAP to correct for spectral overlap in high-resolution continuum source graphite furnace atomic absorption spectrometry},
author = {Flávio V. Nakadi and M. Carmen García-Poyo and Christophe Pécheyran and Martín Resano},
url = {http://dx.doi.org/10.1039/D1JA00233C},
doi = {10.1039/D1JA00233C},
year = {2021},
date = {2021-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {36},
issue = {11},
pages = {2370-2382},
publisher = {The Royal Society of Chemistry},
abstract = {High-resolution continuum source graphite furnace atomic absorption spectrometry HR CS GFAAS provides information about the vicinity of the analytical line, thus effectively transforming a 2-dimension technique (time versus absorbance) into a 3-dimension one (by adding wavelength information), which represents a key advantage when dealing with potential spectral overlaps. Indeed, the occurrence of diatomic molecule absorption often results in high background values in classical AAS, affecting many analyses. The high spectral resolution provided by HR CS AAS in this third dimension enables the use of new tools, first to detect and later to solve this problem. Currently, the software of commercially available HR CS AAS spectrometers is equipped with an algorithm for interference correction, the so-called least-squares background correction (LSBC). Using a spectrum from the interfering species as a correction model, LSBC can correct for the spectral interference by subtracting it. Nevertheless, this approach still poses some problems (e.g., the need to identify the overlapping species). Moreover, there is still a lot of information contained in every measurement that is essentially unused and can help in correcting for spectral overlaps. The time-absorbance profile (TAP) of a species, measured under the same instrumental HR CS AAS conditions using a GF as the atomizer, should be the same at every wavelength measured. Therefore, using a TAP normalized spectrum of the interfering species should be sufficient to subtract it from the normalized absorbance of the atomic line, leaving only the analytical signal of the analyte. This paper proposes the use of such an approach for the first time and discusses in detail how the TAP method can be deployed, without the need to perform any additional measurements or know in advance the nature of the overlapping species. The usefulness of TAP correction for circumventing spectral overlaps and reaching a good agreement with certified/reference values is demonstrated in various situations (e.g., direct determination of Pb in NIST 1570a spinach leaves and NIST 1577b bovine liver, of Ni in NIST 1573 tomato leaves, and of Cu in dried plasma spots produced from whole blood Seronorm™), and its current limitations are highlighted as well.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
García-Poyo, M. Carmen; Ronzani, Anne Laure; Frayret, Jérôme; Bérail, Sylvain; Rello, Luis; García-González, Elena; Lelièvre, Bénédicte; Nakadi, Flávio V.; Aramendía, Maite; Resano, Martín; Pécheyran, Christophe
En: Spectrochimica Acta Part B: Atomic Spectroscopy, vol. 185, pp. 106306, 2021, ISSN: 0584-8547.
@article{GARCIAPOYO2021106306,
title = {Evaluation of electrothermal vaporization for sample introduction aiming at Cu isotopic analysis via multicollector-inductively coupled plasma mass spectrometry},
author = {M. Carmen García-Poyo and Anne Laure Ronzani and Jérôme Frayret and Sylvain Bérail and Luis Rello and Elena García-González and Bénédicte Lelièvre and Flávio V. Nakadi and Maite Aramendía and Martín Resano and Christophe Pécheyran},
url = {https://www.sciencedirect.com/science/article/pii/S0584854721002639},
doi = {https://doi.org/10.1016/j.sab.2021.106306},
issn = {0584-8547},
year = {2021},
date = {2021-01-01},
journal = {Spectrochimica Acta Part B: Atomic Spectroscopy},
volume = {185},
pages = {106306},
abstract = {A new method for Cu isotopic analysis was developed using a commercially available electrothermal vaporization (ETV) device coupled to multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS). The method demonstrated potential for the isotopic analysis of microsamples (e.g., 5 μL) in a biological context. For example, Cu isotopic analysis of NIST 3114 (diluted to 1 mg L−1 Cu) using self-bracketing provided average δ65Cu values of 0.00 ± 0.17‰ (2SD},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
García-Poyo, M. Carmen; Pécheyran, Christophe; Rello, Luis; García-González, Elena; Rodríguez, Sharay Alonso; Nakadi, Flávio V.; Aramendía, Maite; Resano, Martín
En: J. Anal. At. Spectrom., vol. 36, iss. 8, pp. 1666-1677, 2021.
@article{D1JA00155H,
title = {Determination of Cu in blood via direct analysis of dried blood spots using high-resolution continuum source graphite furnace atomic absorption spectrometry},
author = {M. Carmen García-Poyo and Christophe Pécheyran and Luis Rello and Elena García-González and Sharay Alonso Rodríguez and Flávio V. Nakadi and Maite Aramendía and Martín Resano},
url = {http://dx.doi.org/10.1039/D1JA00155H},
doi = {10.1039/D1JA00155H},
year = {2021},
date = {2021-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {36},
issue = {8},
pages = {1666-1677},
publisher = {The Royal Society of Chemistry},
abstract = {The performance of state-of-the-art high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) instrumentation and four novel devices to produce dried blood spots of perfectly defined volumes is evaluated with the aim of developing a simple, direct method for the determination of Cu in blood samples. In all cases, it is feasible to obtain accurate quantitative information using any of the four devices tested (Mitra, HemaXis DB10, Capitainer qDBS and HemaPEN) via simple external calibration with aqueous standards. One of the main differences in the performance of such devices is related to the blanks obtained, such that HemaXis DB10 and HemaPEN are preferred when abnormally low Cu levels (500 μg L−1 or lower), associated with some diseases, need to be determined. The results prove that accurate values with RSD values below 10% can be achieved for these devices even for such Cu levels, while for Capitainer qDBS and, to a higher extent, for Mitra, blank variations will ultimately increase the uncertainty. It is important to stress that analysis of four real samples using both venipuncture and all the DBS specimens showed a very good agreement. Thus, the approach proposed could be readily applied, such that patients with disorders requiring Cu control can prepare their own samples and submit them via postal mail to labs for HR CS GFAAS direct and fast analysis.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Abad-Alvaro, I.; Leite, D.; Bartczak, D.; Cuello-Nunez, S.; Gomez-Gomez, B.; Madrid, Y.; Aramendia, M.; Resano, M.; Goenaga-Infante, H.
En: J. Anal. At. Spectrom., vol. 36, iss. 6, pp. 1180-1192, 2021.
@article{D1JA00068C,
title = {An insight into the determination of size and number concentration of silver nanoparticles in blood using single particle ICP-MS (spICP-MS): feasibility of application to samples relevant to in vivo toxicology studies},
author = {I. Abad-Alvaro and D. Leite and D. Bartczak and S. Cuello-Nunez and B. Gomez-Gomez and Y. Madrid and M. Aramendia and M. Resano and H. Goenaga-Infante},
url = {http://dx.doi.org/10.1039/D1JA00068C},
doi = {10.1039/D1JA00068C},
year = {2021},
date = {2021-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {36},
issue = {6},
pages = {1180-1192},
publisher = {The Royal Society of Chemistry},
abstract = {Toxicological studies concerning nanomaterials in complex biological matrices usually require a carefully designed workflow that involves handling, transportation and preparation of a large number of samples without affecting the nanoparticle (NP) characteristics, as well as measurement methods that enable their reliable characterisation. This work describes method development for the determination of number concentration and size of silver nanoparticles (AgNP) in blood for the purpose of application to the typical workflow of an in vivo toxicology assessment involving blood-containing AgNP and Ag(i) leached out from medical devices. A systematic comparison of single particle detection using millisecond versus microsecond dwell times in the presence of different ionic Ag [Ag(i)]-to-AgNP ratios by spICP-MS was undertaken to achieve sufficient selectivity for the determination of NP number concentration. This was achieved for the first time in a complex media such as 2.5% tetramethylammonium hydroxide (TMAH)/0.1% Triton X-100 (v/v) diluent, which was proven to preserve nanoparticle stability upon 8 days of storage following AgNP quantitative extraction from the blood matrix. The potential of microsecond dwell time for improved discrimination of AgNP (40 nm) from Ag(i) was demonstrated for ionic to nanoparticle ratios [Ag(i)/AgNP] of up to 106-fold. For NP sizing, a systematic study of the impact of matrix-matched ionic calibration on the derived particle size by spICP-MS is also described. Three different ionic calibration media including 1% HNO3 (v/v), 1 mM trisodium citrate and 2.5% TMAH/0.1% Triton X-100 (v/v) were tested. Student t-test evidenced statistically significant differences between the slope of the calibration curve of Ag(i) in TMAH/Triton X-100 compared to HNO3 and trisodium citrate matrices, whereas no significant differences were found between the two latter media. Moreover, a good agreement was found between the particle diameter derived from spICP-MS following ionic calibration in TMAH/Triton X-100 and the diameter obtained with transmission electron microscopy (TEM), demonstrating the importance of matrix-matched calibration for NP size determination in a complex matrix using spICP-MS. Number concentration recovery measurements on blood samples spiked with AgNP and size measurements both using spICP-MS demonstrated the feasibility of the methodology developed here for potential future application to AgNP characterisation in toxicology research.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
García-Poyo, M. Carmen; Bérail, Sylvain; Ronzani, Anne Laure; Rello, Luis; García-González, Elena; Lelièvre, Bénédicte; Cales, Paul; Nakadi, Flavio V.; Aramendía, Maite; Resano, Martín; Pécheyran, Christophe
En: J. Anal. At. Spectrom., vol. 36, iss. 5, pp. 968-980, 2021.
@article{D0JA00494D,
title = {Laser ablation of microdroplets for copper isotopic analysis via MC-ICP-MS. Analysis of serum microsamples for the diagnosis and follow-up treatment of Wilson's disease},
author = {M. Carmen García-Poyo and Sylvain Bérail and Anne Laure Ronzani and Luis Rello and Elena García-González and Bénédicte Lelièvre and Paul Cales and Flavio V. Nakadi and Maite Aramendía and Martín Resano and Christophe Pécheyran},
url = {http://dx.doi.org/10.1039/D0JA00494D},
doi = {10.1039/D0JA00494D},
year = {2021},
date = {2021-01-01},
journal = {J. Anal. At. Spectrom.},
volume = {36},
issue = {5},
pages = {968-980},
publisher = {The Royal Society of Chemistry},
abstract = {Cu isotopic analysis can provide valuable insight when investigating Wilson's disease (WD), but one of the problems related to this type of study is that usually low sample volumes are available and/or low Cu concentrations are found in these samples. This paper presents a new approach for Cu isotope ratio determination that requires only 1 μL of pre-treated serum sample per replicate (after Cu separation and preconcentration to a Cu concentration range between 0.3 and 4 mg L−1). Cu determination was carried out by direct μ-injection of 1 μL of pretreated serum samples into an ICP-MS, offering a LOD of 3 μg L−1. For Cu isotopic analysis, the method presented is based on micro-volume deposition on a pure silicon wafer and subsequent ablation analysis by fsLA-MC-ICP-MS. Cu isotopic analysis of NIST 3114 at 1 mg L−1 Cu concentration with the self-bracketing method provided average δ65Cu values of −0.01 ± 0.19‰ (2SD) and an internal precision value of 517 ppm. This method was deployed for the analysis of serum samples from WD patients under different treatments, as well as healthy newborns and patients with other liver disorders. The results seem to link decreased δ65Cu values to Cu release from the liver, further demonstrating the potential of this type of analysis in the biomedical context.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}