Teléfono: +34 976 761 634 / +34 976 761 175
Email: mresano@unizar.es
Dirección: c/Pedro Cerbuna 12, Universidad de Zaragoza, Facultad de Ciencias, Departamento de Química Analítica – Zaragoza (España)
SOBRE MÍ
El Dr. Martín Resano Ezcaray (Doctor por la Universidad de Zaragoza en 1999; Post-Doc en la Universidad de Gante (Bélgica)) es Catedrático de la Universidad de Zaragoza donde dirige el grupo de investigación MARTE (Métodos de Análisis Rápido con Técnicas Espectroscópicas, Referencia DGA E43_20R) desde 2008.
El Dr. M. Resano ha presidido el Comité Editorial (Chair of Editorial Board) de la revista Journal of Analytical Atomic Spectrometry entre Julio de 2016 y Julio de 2020 y es Fellow Member de la Royal Society of Chemistry.Su trabajo ha sido galardonado (26/03/2015) con el Premio Bunsen-Kirchhoff que otorga el grupo de Espectroscopía Analítica (AK DAAS) de la Sociedad Química Alemana (GDCh). Más información disponible en los enlaces a sus identificadores científicos.
PUBLICACIONES
2025
Bazo, Antonio; Bolea-Fernandez, Eduardo; Rua-Ibarz, Ana; Aramendía, Maite; Resano, Martín
En: Anal. Chem., 2025, ISSN: 1520-6882.
@article{nokey,
title = {Ions with Ions, Entities with Entities: A Proof-of-Concept Study Using the SELM-1 Yeast Certified Reference Material for Intra- and Extracellular Se Quantification via Single-Cell ICP-Mass Spectrometry},
author = {Antonio Bazo and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Maite Aramendía and Martín Resano},
url = {https://pubs.acs.org/doi/10.1021/acs.analchem.5c01588},
doi = {https://doi.org/10.1021/acs.analchem.5c01588},
issn = {1520-6882},
year = {2025},
date = {2025-06-07},
urldate = {2025-06-07},
journal = {Anal. Chem.},
abstract = {In this work, two novel nanoparticle (NP)-based calibration strategies, external calibration and a relative method, have been explored for single-cell ICP-mass spectrometry (SC-ICP-MS) analysis. The fundamental principle of these methods is to rely on individual entities (well-characterized NPs of the target analyte) for calibration rather than on ionic standard solutions. The performance of the NP-based calibration approaches has been compared to that of the reference method (particle size with AuNP standards). In addition to the intracellular Se content (mass per individual cell), the extracellular Se (dissolved fraction) was also determined directly and simultaneously using the average background from the SC-ICP-MS time-resolved signal. The figures-of-merit of the methods developed have been evaluated by relying on the analysis of the SELM-1 cell-certified reference material, consisting of Se-enriched yeast cells, and certified for its total Se content (intracellular + extracellular Se). All methods successfully determined the Se elemental contents, but an improvement in accuracy and precision was observed for the NP-based methods compared to the reference one. Furthermore, the NP-based methods were found to be less time-consuming, more straightforward, and more user-friendly in terms of calculations. These results open new avenues for calibration in quantitative SC-ICP-MS analysis and call for a fundamental change in the methodology, where the determination of ionic contents is based on the use of ionic standard solutions for calibration, while the determination of elemental contents in discrete micro/nanoentities, such as cells, should ideally be based on calibration using standard entities, thus avoiding the need to calculate a transport efficiency coefficient.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
In this work, two novel nanoparticle (NP)-based calibration strategies, external calibration and a relative method, have been explored for single-cell ICP-mass spectrometry (SC-ICP-MS) analysis. The fundamental principle of these methods is to rely on individual entities (well-characterized NPs of the target analyte) for calibration rather than on ionic standard solutions. The performance of the NP-based calibration approaches has been compared to that of the reference method (particle size with AuNP standards). In addition to the intracellular Se content (mass per individual cell), the extracellular Se (dissolved fraction) was also determined directly and simultaneously using the average background from the SC-ICP-MS time-resolved signal. The figures-of-merit of the methods developed have been evaluated by relying on the analysis of the SELM-1 cell-certified reference material, consisting of Se-enriched yeast cells, and certified for its total Se content (intracellular + extracellular Se). All methods successfully determined the Se elemental contents, but an improvement in accuracy and precision was observed for the NP-based methods compared to the reference one. Furthermore, the NP-based methods were found to be less time-consuming, more straightforward, and more user-friendly in terms of calculations. These results open new avenues for calibration in quantitative SC-ICP-MS analysis and call for a fundamental change in the methodology, where the determination of ionic contents is based on the use of ionic standard solutions for calibration, while the determination of elemental contents in discrete micro/nanoentities, such as cells, should ideally be based on calibration using standard entities, thus avoiding the need to calculate a transport efficiency coefficient.
Nakadi, Flávio V.; Garcia-Garcia, Alicia; Rua-Ibarz, Ana; Resano, Martín
LAMIS in the gas phase: A new approach for obtaining Ca elemental and isotopic information via CaF molecule formation Artículo de revista
En: Talanta, vol. 292, pp. 127920, 2025, ISSN: 0039-9140.
@article{NAKADI2025127920,
title = {LAMIS in the gas phase: A new approach for obtaining Ca elemental and isotopic information via CaF molecule formation},
author = {Flávio V. Nakadi and Alicia Garcia-Garcia and Ana Rua-Ibarz and Martín Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0039914025004102},
doi = {https://doi.org/10.1016/j.talanta.2025.127920},
issn = {0039-9140},
year = {2025},
date = {2025-01-01},
urldate = {2025-01-01},
journal = {Talanta},
volume = {292},
pages = {127920},
abstract = {This work introduces a novel method for generating the calcium monofluoride (CaF) diatomic molecule by adding the molecule-forming reagent in the gaseous phase (a methyl fluoride-argon mixture), in order to perform laser-induced breakdown spectroscopy (LIBS) and laser ablation molecular isotopic spectrometry (LAMIS) measurements. By optimizing the instrumental parameters, CaF molecule formation was successfully achieved within the plasma plume, upon ablation of dried liquid samples. The isotopic shift for the X2Σ→A2Π (0,1) CaF vibronic transition at 583.0 nm was calculated to be 292.3 pm. The method proved capable of providing quantitative information for determining calcium concentrations in real samples, such as tap water and skimmed milk, using internal standardization (with Sr as internal standard; limit of detection, LOD, 20 mg L−1) and isotope dilution (which can be applied from 400 mg L−1on), respectively. Partial least squares regression (PLS) analysis was employed to enhance the quality of the isotopic data. The Ca concentration found in the tap water was 47 ± 16 mg L−1 (reference flame atomic absorption spectrometry, FAAS, value: 59 ± 0.2 mg L−1), and 1100 ± 140 mg L−1 for the skimmed milk (reference FAAS value: 1240 ± 120 mg L−1). No significant difference between LIBS and FAAS results could be established using a t-test at the 95% confidence level. Overall, this novel approach allows for the determination of calcium in terms of both the elemental concentration and the isotopic composition, thus broadening the applicability of LIBS (e.g., for tracer experiments, besides the already mentioned application of isotope dilution).},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This work introduces a novel method for generating the calcium monofluoride (CaF) diatomic molecule by adding the molecule-forming reagent in the gaseous phase (a methyl fluoride-argon mixture), in order to perform laser-induced breakdown spectroscopy (LIBS) and laser ablation molecular isotopic spectrometry (LAMIS) measurements. By optimizing the instrumental parameters, CaF molecule formation was successfully achieved within the plasma plume, upon ablation of dried liquid samples. The isotopic shift for the X2Σ→A2Π (0,1) CaF vibronic transition at 583.0 nm was calculated to be 292.3 pm. The method proved capable of providing quantitative information for determining calcium concentrations in real samples, such as tap water and skimmed milk, using internal standardization (with Sr as internal standard; limit of detection, LOD, 20 mg L−1) and isotope dilution (which can be applied from 400 mg L−1on), respectively. Partial least squares regression (PLS) analysis was employed to enhance the quality of the isotopic data. The Ca concentration found in the tap water was 47 ± 16 mg L−1 (reference flame atomic absorption spectrometry, FAAS, value: 59 ± 0.2 mg L−1), and 1100 ± 140 mg L−1 for the skimmed milk (reference FAAS value: 1240 ± 120 mg L−1). No significant difference between LIBS and FAAS results could be established using a t-test at the 95% confidence level. Overall, this novel approach allows for the determination of calcium in terms of both the elemental concentration and the isotopic composition, thus broadening the applicability of LIBS (e.g., for tracer experiments, besides the already mentioned application of isotope dilution).
Bazo, Antonio; Bolea-Fernandez, Eduardo; Billimoria, Kharmen; Rua-Ibarz, Ana; Aramendía, Maite; Menero-Valdés, Paula; Morley, Jack; Neves, Sara; Sánchez-Cachero, Armando; Goenaga-Infante, Heidi; Resano, Martín
A novel particle mass calibration strategy for the quantification of AuNPs in single cancer cells via laser ablation ICP-mass spectrometry. A case study Artículo de revista
En: J. Anal. At. Spectrom., pp. -, 2025.
@article{D5JA00253B,
title = {A novel particle mass calibration strategy for the quantification of AuNPs in single cancer cells via laser ablation ICP-mass spectrometry. A case study},
author = {Antonio Bazo and Eduardo Bolea-Fernandez and Kharmen Billimoria and Ana Rua-Ibarz and Maite Aramendía and Paula Menero-Valdés and Jack Morley and Sara Neves and Armando Sánchez-Cachero and Heidi Goenaga-Infante and Martín Resano},
url = {http://dx.doi.org/10.1039/D5JA00253B},
doi = {10.1039/D5JA00253B},
year = {2025},
date = {2025-01-01},
urldate = {2025-01-01},
journal = {J. Anal. At. Spectrom.},
pages = {-},
publisher = {The Royal Society of Chemistry},
abstract = {Laser ablation ICP-mass spectrometry (LA-ICP-MS) has developed as a powerful tool for elemental quantitative analysis of individual cells, assuring that the content of each cell is analyzed individually. However, this technique is still limited by the difficulties associated with calibration using solid standards. This work proposes a particle mass calibration strategy that is independent of both the properties and thickness of the gelatin films used for calibration, overcoming a significant drawback of previously established methods. The fundamental principle of this strategy relies on the individual ablation of nanoparticles (NPs) of well-characterized size that are embedded in the films, so that their mass can be directly used for calibration without the need to calculate their exact concentration within the gelatin. The performance of the newly developed method was compared to that of the previously reported approaches (ionic and particle number calibration) in terms of linearity and homogeneity between different films prepared from the same gelatin solution. As a case study, the three calibration strategies were used for the quantitative analysis of HeLa cancer cells exposed to AuNPs. In parallel, in-suspension single-cell (SC) ICP-MS Au data were obtained and used as reference for comparison with the three LA-SC-ICP-MS strategies. The results obtained with the novel particle mass approach demonstrated better accuracy and repeatability over three different working sessions, addressing key limitations and providing a robust and reliable method for quantitative LA-SC-ICP-MS analysis. The particle mass method holds promise for quantitative LA-ICP-MS analysis of samples beyond NP-exposed cells, such as biological tissues.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Laser ablation ICP-mass spectrometry (LA-ICP-MS) has developed as a powerful tool for elemental quantitative analysis of individual cells, assuring that the content of each cell is analyzed individually. However, this technique is still limited by the difficulties associated with calibration using solid standards. This work proposes a particle mass calibration strategy that is independent of both the properties and thickness of the gelatin films used for calibration, overcoming a significant drawback of previously established methods. The fundamental principle of this strategy relies on the individual ablation of nanoparticles (NPs) of well-characterized size that are embedded in the films, so that their mass can be directly used for calibration without the need to calculate their exact concentration within the gelatin. The performance of the newly developed method was compared to that of the previously reported approaches (ionic and particle number calibration) in terms of linearity and homogeneity between different films prepared from the same gelatin solution. As a case study, the three calibration strategies were used for the quantitative analysis of HeLa cancer cells exposed to AuNPs. In parallel, in-suspension single-cell (SC) ICP-MS Au data were obtained and used as reference for comparison with the three LA-SC-ICP-MS strategies. The results obtained with the novel particle mass approach demonstrated better accuracy and repeatability over three different working sessions, addressing key limitations and providing a robust and reliable method for quantitative LA-SC-ICP-MS analysis. The particle mass method holds promise for quantitative LA-ICP-MS analysis of samples beyond NP-exposed cells, such as biological tissues.
Bazo, Antonio; López-Villellas, Lorién; Mataloni, Matilde; Bolea-Fernandez, Eduardo; Rua-Ibarz, Ana; Grotti, Marco; Aramendía, Maite; Resano, Martín
Improving detection and figures of merit in single-particle inductively coupled plasma-mass spectrometry via transient event heights Artículo de revista
En: Analytica Chimica Acta, vol. 1378, pp. 344694, 2025, ISSN: 0003-2670.
@article{BAZO2025344694,
title = {Improving detection and figures of merit in single-particle inductively coupled plasma-mass spectrometry via transient event heights},
author = {Antonio Bazo and Lorién López-Villellas and Matilde Mataloni and Eduardo Bolea-Fernandez and Ana Rua-Ibarz and Marco Grotti and Maite Aramendía and Martín Resano},
url = {https://www.sciencedirect.com/science/article/pii/S0003267025010888},
doi = {https://doi.org/10.1016/j.aca.2025.344694},
issn = {0003-2670},
year = {2025},
date = {2025-01-01},
urldate = {2025-01-01},
journal = {Analytica Chimica Acta},
volume = {1378},
pages = {344694},
abstract = {Background
Single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is a powerful method for characterizing micro- and nanoparticulate materials. The technique primarily relies on the linear relationship between the integrated intensities of individual events (peak areas) and the analyte mass, though transit times (peak widths) have also been used for quantitative purposes. This work (1) evaluates the potential of using peak heights as analytical signals in SP-ICP-MS, (2) introduces a new method for determining peak heights, and (3) explores scenarios in which peak height offers added value over the commonly used SP-ICP-MS signals.
Results
A new method was proposed to estimate peak height values in SP-ICP-MS accurately. The cumulative intensity across consecutive dwell times was modeled using a third-degree polynomial, from which the adjusted peak height was derived. This approach reduces the uncertainty associated with using raw maximum intensity values, yielding NP distributions comparable to those obtained via integrated intensities. The effect of dwell time on peak height was also evaluated. An optimal range (50 μs–200 μs) was identified, where a linear relationship was observed between the peak height and the square of the NP diameter. Within this range, peak height showed the lowest bias when characterizing smaller NPs, indicating the potential to improve the limit of quantification (LoQ). Additionally, peak heights proved helpful in determining the limit of detection (LoD) and setting appropriate threshold values for data processing, thereby helping to flag incorrect resultsand addressing a challenge in SP-ICP-MS analysis.
Significance
This is the first study to evaluate peak height as an analytical signal in SP-ICP-MS. The results highlight its advantages in specific applications, such as sizing NPs near the LoD, and in supporting the more reliable use of other signals, such as peak areas, by helping to identify incorrect threshold selection that could lead to biased distributions. Finally, monitoring peak heights allows for a more realistic and assumption-free determination of the LoD.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Background
Single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is a powerful method for characterizing micro- and nanoparticulate materials. The technique primarily relies on the linear relationship between the integrated intensities of individual events (peak areas) and the analyte mass, though transit times (peak widths) have also been used for quantitative purposes. This work (1) evaluates the potential of using peak heights as analytical signals in SP-ICP-MS, (2) introduces a new method for determining peak heights, and (3) explores scenarios in which peak height offers added value over the commonly used SP-ICP-MS signals.
Results
A new method was proposed to estimate peak height values in SP-ICP-MS accurately. The cumulative intensity across consecutive dwell times was modeled using a third-degree polynomial, from which the adjusted peak height was derived. This approach reduces the uncertainty associated with using raw maximum intensity values, yielding NP distributions comparable to those obtained via integrated intensities. The effect of dwell time on peak height was also evaluated. An optimal range (50 μs–200 μs) was identified, where a linear relationship was observed between the peak height and the square of the NP diameter. Within this range, peak height showed the lowest bias when characterizing smaller NPs, indicating the potential to improve the limit of quantification (LoQ). Additionally, peak heights proved helpful in determining the limit of detection (LoD) and setting appropriate threshold values for data processing, thereby helping to flag incorrect resultsand addressing a challenge in SP-ICP-MS analysis.
Significance
This is the first study to evaluate peak height as an analytical signal in SP-ICP-MS. The results highlight its advantages in specific applications, such as sizing NPs near the LoD, and in supporting the more reliable use of other signals, such as peak areas, by helping to identify incorrect threshold selection that could lead to biased distributions. Finally, monitoring peak heights allows for a more realistic and assumption-free determination of the LoD.
Single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is a powerful method for characterizing micro- and nanoparticulate materials. The technique primarily relies on the linear relationship between the integrated intensities of individual events (peak areas) and the analyte mass, though transit times (peak widths) have also been used for quantitative purposes. This work (1) evaluates the potential of using peak heights as analytical signals in SP-ICP-MS, (2) introduces a new method for determining peak heights, and (3) explores scenarios in which peak height offers added value over the commonly used SP-ICP-MS signals.
Results
A new method was proposed to estimate peak height values in SP-ICP-MS accurately. The cumulative intensity across consecutive dwell times was modeled using a third-degree polynomial, from which the adjusted peak height was derived. This approach reduces the uncertainty associated with using raw maximum intensity values, yielding NP distributions comparable to those obtained via integrated intensities. The effect of dwell time on peak height was also evaluated. An optimal range (50 μs–200 μs) was identified, where a linear relationship was observed between the peak height and the square of the NP diameter. Within this range, peak height showed the lowest bias when characterizing smaller NPs, indicating the potential to improve the limit of quantification (LoQ). Additionally, peak heights proved helpful in determining the limit of detection (LoD) and setting appropriate threshold values for data processing, thereby helping to flag incorrect resultsand addressing a challenge in SP-ICP-MS analysis.
Significance
This is the first study to evaluate peak height as an analytical signal in SP-ICP-MS. The results highlight its advantages in specific applications, such as sizing NPs near the LoD, and in supporting the more reliable use of other signals, such as peak areas, by helping to identify incorrect threshold selection that could lead to biased distributions. Finally, monitoring peak heights allows for a more realistic and assumption-free determination of the LoD.
2024
Chan, George C. -Y.; Hieftje, Gary M.; Omenetto, Nicoló; Axner, Ove; Bengtson, Arne; Bings, Nicolas H.; Blades, Michael W.; Bogaerts, Annemie; Bolshov, Mikhail A.; Broekaert, José A. C.; Chan, WingTat; Costa-Fernández, José M.; Crouch, Stanley R.; Giacomo, Alessandro De; D’Ulivo, Alessandro; Engelhard, Carsten; Falk, Heinz; Farnsworth, Paul B.; Florek, Stefan; Gamez, Gerardo; Gornushkin, Igor B.; Günther, Detlef; Hahn, David W.; Hang, Wei; Hoffmann, Volker; Jakubowski, Norbert; Karanassios, Vassili; Koppenaal, David W.; Marcus, R. Kenneth; Noll, Reinhard; Olesik, John W.; Palleschi, Vincenzo; Panne, Ulrich; Pisonero, Jorge; Ray, Steven J.; Resano, Martín; Russo, Richard E.; Scheeline, Alexander; Smith, Benjamin W.; Sturgeon, Ralph E.; Todolí, José-Luis; Tognoni, Elisabetta; Vanhaecke, Frank; Webb, Michael R.; Winefordner, James D.; Yang, Lu; Yu, Jin; Zhang, Zhanxia
EXPRESS: Landmark Publications in Analytical Atomic Spectrometry: Fundamentals and Instrumentation Development Artículo de revista
En: Applied Spectroscopy, vol. 0, no ja, pp. 00037028241263567, 2024, (PMID: 38881037).
@article{doi:10.1177/00037028241263567b,
title = {EXPRESS: Landmark Publications in Analytical Atomic Spectrometry: Fundamentals and Instrumentation Development},
author = {George C. -Y. Chan and Gary M. Hieftje and Nicoló Omenetto and Ove Axner and Arne Bengtson and Nicolas H. Bings and Michael W. Blades and Annemie Bogaerts and Mikhail A. Bolshov and José A. C. Broekaert and WingTat Chan and José M. Costa-Fernández and Stanley R. Crouch and Alessandro De Giacomo and Alessandro D’Ulivo and Carsten Engelhard and Heinz Falk and Paul B. Farnsworth and Stefan Florek and Gerardo Gamez and Igor B. Gornushkin and Detlef Günther and David W. Hahn and Wei Hang and Volker Hoffmann and Norbert Jakubowski and Vassili Karanassios and David W. Koppenaal and R. Kenneth Marcus and Reinhard Noll and John W. Olesik and Vincenzo Palleschi and Ulrich Panne and Jorge Pisonero and Steven J. Ray and Martín Resano and Richard E. Russo and Alexander Scheeline and Benjamin W. Smith and Ralph E. Sturgeon and José-Luis Todolí and Elisabetta Tognoni and Frank Vanhaecke and Michael R. Webb and James D. Winefordner and Lu Yang and Jin Yu and Zhanxia Zhang},
url = {https://doi.org/10.1177/00037028241263567},
doi = {10.1177/00037028241263567},
year = {2024},
date = {2024-06-16},
urldate = {2024-06-16},
journal = {Applied Spectroscopy},
volume = {0},
number = {ja},
pages = {00037028241263567},
abstract = {The almost-two-centuries history of spectrochemical analysis has generated a body of literature so vast that it has become nearly intractable for experts, much less for those wishing to enter the field. Authoritative, focused reviews help to address this problem but become so granular that the overall directions of the field are lost. This broader perspective can be provided partially by general overviews but then the thinking, experimental details, theoretical underpinnings and instrumental innovations of the original work must be sacrificed. In the present compilation, this dilemma is overcome by assembling the most impactful publications in the area of analytical atomic spectrometry. Each entry was proposed by at least one current expert in the field and supported by a narrative that justifies its inclusion. The entries were then assembled into a coherent sequence and returned to contributors for a round-robin review.},
note = {PMID: 38881037},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The almost-two-centuries history of spectrochemical analysis has generated a body of literature so vast that it has become nearly intractable for experts, much less for those wishing to enter the field. Authoritative, focused reviews help to address this problem but become so granular that the overall directions of the field are lost. This broader perspective can be provided partially by general overviews but then the thinking, experimental details, theoretical underpinnings and instrumental innovations of the original work must be sacrificed. In the present compilation, this dilemma is overcome by assembling the most impactful publications in the area of analytical atomic spectrometry. Each entry was proposed by at least one current expert in the field and supported by a narrative that justifies its inclusion. The entries were then assembled into a coherent sequence and returned to contributors for a round-robin review.