Publicaciones

@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{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}

}

@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}

}

@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},

urldate = {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}

}

@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}

}

@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}

}

@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}

}

@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}

}

@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}

}