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Platinum nanoparticles synthesized by laser ablation in water and their use as substrates for the soft laser desorption/ionization of polymers and peptides Maite Cueto 1* , F. Gámez 2 , A. R. Hortal 2 , P. Hurtado 2 , B. Martínez-Haya 2 M. Sanz 3 , M. Oujja 3 , M. Castillejo 3 1 Instituto de Estructura de la Materia CSIC, Madrid (Spain) 2 Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, 41013 Seville (Spain) 3 Instituto de Química Física Rocasolano CSIC , Madrid (Spain) * E-mail: [email protected] - The object of this work is the synthesis of platinum nanoparticles and the study of their efficiency as substrates for laser desorption/ionization (LDI) of model analytes. - Platinum stands out among the noble metals as a nanostructured assisted LDI (NALDI) active substrate because of its low heat conductivity and high melting temperature [1]. - We have synthesized Platinum nanoparticles by high energy pulsed laser ablation of Pt foil in aqueous solution. - Different Nd:YAG laser wavelengths (266, 532, 1064 nm) and stabilizing agents (PEG, PVA, citrate) have been used to control the nanoparticle size and crystallinity [2,3]. - Pt nanoparticles with single and bimodal size distributions (ranging 2-30 nm) and of spherical and rod-like shape have been obtained. - The nanoparticles have been tested as active substrates for the soft laser desorption/ionization (NALDI-MS) of a synthetic polymer (polyethylenglycol PEG600) and a peptide (Angiotensin I). - The NALDI-MS experiments were performed in positive-ion mode with a commercial time-of-flight mass spectrometer (UltrafleXtreme, Bruker, 355nm laser source) and demonstrate that Platinum nanoparticles provide a good sensitivity for the detection of these model analytes. - The best overall NALDI-MS performance was found for nanoparticles with sizes 2-10 nm, produced with 1064 nm laser pulses, in water or with a light stabilizing agent such as citrate. Summary Experimental Details [1] T. Yonezawa, H. Kawasaki, A. Tarui, T. Watanabe, R. Arakawa, T. Shimada, F. Mafuné, Analytical Sciences, 25 (3), 339-347 (2009). [2] W. T. Nichols, T. Sasaki, N. Koshizaki, Journal of Applied Physics, 100, 114911-114913 (2006). [3] M. Cueto, M. Sanz, M. Oujja, F. Gámez, B. Martínez-Haya, M. Castillejo, Journal of Physical Chemistry C, 115, 22217–22224 (2011). References Funding from the FEDER-Andalucia2007-2013 through projects P07-FQM-02600 and P09-FQM-4938 . Funding from MICINN under Projects CTQ2010-15680 and CONSOLIDER CSD2007-00058, and Programa Geomateriales (CAM, S2009/Mat-1629). We thank GEMPPO at the IEM-CSIC for the use of the HRTEM and CITIUS from Universidad de Sevilla for the use of the TEM equipment. Acknowledgements Q-switched Nd:YAG laser (Quantel, Brilliant B),6 ns FWHM, operating at 10 Hz during 15 min. Laser fluences of 7, 3.5, and 1.5 Jcm -2 , close to the ablation threshold, were employed at the respective wavelengths of 1064, 532 and 266 nm. - Bimodal size distribution : Small size component is presumably associated with a thermal vaporization mechanism and large size component to an explosive ablation mechanism, enhanced at the longer ablation wavelengths. - Short wavelength ablation yields crystalline NPs of small size and large crystalline nanorods (10x70 nm 2 ), especially when PEG and PVA are employed. - The smallest NPs were obtained in citrate solutions due to the more efficient coating of the ablated material. HRTEM Production of nanoparticles by Laser ablation in water TOF-MS (UltrafleXtreme, Bruker), Nd:YAG laser at 355 nm, operating at 1 kHz. Mass spectra averaged over 2000 laser shots. NALDI Experiments Size distributions Nanoparticles average size (nm) crystallinity Size distributions Nanoparticles average size (nm) Crystallinity Conclusions - The best NALDI-MS performances were obtained with Platinum Nanoparticles produced at 1064 nm in pure water and citrate as stabilizing agent. This result is attributed, on one hand, to the adequate size of the nanoparticles for the analyte adsorption and for a more efficient analyte desorption due to plasmonic excitacion. On the other hand, light stabilizing agents such as citrate provide a homogeneous and close interaction between the nanoparticle and the analyte better than polymers such as PVA, that act as molecular spacers. NPs synthesized in water : 18B at 1064 nm NPs 17B at 532 nm NPs 45B at 266 nm 1300 1320 1340 0 5000 10000 15000 20000 25000 Sample plate 1 Sample plate 2 Sample plate 3 Average [Ang+2Na-H] + [Ang-K] + [Ang-Na] + [Ang-H] + Ang-Np25B-Na 5-5-5 45% Intensity/ a.u. m/z 1300 1320 1340 0 4000 8000 [Ang+2Na-H] + [Ang-K] + [Ang-Na] + [Ang-H] + Sample plate 1 Sample plate 2 Sample plate 3 Average Ang-Np50B-Na 5-2-5 45% m/z Intensity/ a.u. 1300 1320 1340 0 5000 10000 [Ang+2Na-H] + [Ang-K] + [Ang-Na] + [Ang-H] + Sample plate 1 Sample plate 2 Sample plate 3 Average Ang-Np9B-Na 5-5-5 45% m/z Intensity/ a.u. 200 300 400 500 600 700 800 900 0 5000 10000 15000 20000 m/z Intensity/ a.u. PEG-Np18B-Na 5-7-5_35% Sample plate 1 Sample plate 2 Sample plate 3 Average PEG-Na + PEG-K + 8 9 10 11 12 13 14 15 16 17 18 19 200 300 400 500 600 700 800 900 0 5000 10000 15000 20000 m/z Intensity/ a.u. PEG-Np17B-Na 5-7-5_35% Sample plate 1 Sample plate 2 Sample plate 3 Average PEG-Na + PEG-K + 19 18 17 16 15 14 13 12 11 10 9 8 7 200 400 600 800 0 2000 4000 6000 PEG-Np45B-Na 5-2-5_35% Intensity/ a.u. m/z Sample plate 1 Sample plate 2 Sample plate 3 Average PEG-Na + PEG-K + 12 13 14 15 16 17 18 19 11 10 9 8 7 NPs synthesized in citrate : 25B at 1064 nm NPs 9B at 532 nm NPs50B at 266 nm
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Platinum nanoparticles synthesized by laser ablation in water and their use as substrates for the soft laser desorption/ionization of polymers and peptides
Maite Cueto1*, F. Gámez2, A. R. Hortal2, P. Hurtado2, B. Martínez-Haya2 M. Sanz3, M. Oujja3, M. Castillejo3
1 Instituto de Estructura de la Materia CSIC, Madrid (Spain)
2 Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, 41013 Seville (Spain) 3 Instituto de Química Física Rocasolano CSIC , Madrid (Spain)
*E-mail: [email protected]
- The object of this work is the synthesis of platinum nanoparticles and the study of their efficiency as substrates for laser desorption/ionization (LDI) of model analytes. - Platinum stands out among the noble metals as a nanostructured assisted LDI (NALDI) active substrate because of its low heat conductivity and high melting temperature [1]. - We have synthesized Platinum nanoparticles by high energy pulsed laser ablation of Pt foil in aqueous solution. - Different Nd:YAG laser wavelengths (266, 532, 1064 nm) and stabilizing agents (PEG, PVA, citrate) have been used to control the nanoparticle size and crystallinity [2,3]. - Pt nanoparticles with single and bimodal size distributions (ranging 2-30 nm) and of spherical and rod-like shape have been obtained. - The nanoparticles have been tested as active substrates for the soft laser desorption/ionization (NALDI-MS) of a synthetic polymer (polyethylenglycol PEG600) and a peptide (Angiotensin I). - The NALDI-MS experiments were performed in positive-ion mode with a commercial time-of-flight mass spectrometer (UltrafleXtreme, Bruker, 355nm laser source) and demonstrate that Platinum nanoparticles provide a good sensitivity for the detection of these model analytes. - The best overall NALDI-MS performance was found for nanoparticles with sizes 2-10 nm, produced with 1064 nm laser pulses, in water or with a light stabilizing agent such as citrate.
Summary
Experimental Details
[1] T. Yonezawa, H. Kawasaki, A. Tarui, T. Watanabe, R. Arakawa, T. Shimada, F. Mafuné, Analytical Sciences, 25 (3), 339-347 (2009). [2] W. T. Nichols, T. Sasaki, N. Koshizaki, Journal of Applied Physics, 100, 114911-114913 (2006). [3] M. Cueto, M. Sanz, M. Oujja, F. Gámez, B. Martínez-Haya, M. Castillejo, Journal of Physical Chemistry C, 115, 22217–22224 (2011).
References
Funding from the FEDER-Andalucia2007-2013 through projects P07-FQM-02600 and P09-FQM-4938 . Funding from MICINN under Projects CTQ2010-15680 and CONSOLIDER CSD2007-00058, and Programa Geomateriales (CAM, S2009/Mat-1629). We thank GEMPPO at the IEM-CSIC for the use of the HRTEM and CITIUS from Universidad de Sevilla for the use of the TEM equipment.
Acknowledgements
Q-switched Nd:YAG laser (Quantel, Brilliant B),6 ns FWHM, operating at 10 Hz during 15 min. Laser fluences of 7, 3.5, and 1.5 Jcm-2, close to the ablation threshold, were employed at the respective wavelengths of 1064, 532 and 266 nm.
- Bimodal size distribution: Small size component is presumably associated with a thermal vaporization mechanism and large size component to an explosive ablation mechanism, enhanced at the longer ablation wavelengths.
- Short wavelength ablation yields crystalline NPs of small size and large crystalline nanorods (10x70 nm2), especially when PEG and PVA are employed.
- The smallest NPs were obtained in citrate solutions due to the more efficient coating of the ablated material.
HRTEM
Production of nanoparticles by Laser ablation in water
TOF-MS (UltrafleXtreme, Bruker), Nd:YAG laser at 355 nm, operating at 1 kHz. Mass spectra averaged over 2000 laser shots.
NALDI Experiments
Size distributions Nanoparticles average size (nm) crystallinity Size distributions Nanoparticles average size (nm) Crystallinity
Conclusions
- The best NALDI-MS performances were obtained with Platinum Nanoparticles produced at 1064 nm in pure water and citrate as stabilizing agent. This result is attributed, on one hand, to the adequate size of the nanoparticles for the analyte adsorption and for a more efficient analyte desorption due to plasmonic excitacion. On the other hand, light stabilizing agents such as citrate provide a homogeneous and close interaction between the nanoparticle and the analyte better than polymers such as PVA, that act as molecular spacers.
NPs synthesized in water : 18B at 1064 nm NPs 17B at 532 nm NPs 45B at 266 nm
1300 1320 1340
0
5000
10000
15000
20000
25000
Sample plate 1
Sample plate 2
Sample plate 3
Average
[Ang+2Na-H]+
[Ang-K]+
[Ang-Na]+
[Ang-H]+
Ang-Np25B-Na 5-5-5 45%
Inte
nsity/ a
.u.
m/z
1300 1320 1340
0
4000
8000
[Ang+2Na-H]+
[Ang-K]+
[Ang-Na]+
[Ang-H]+
Sample plate 1
Sample plate 2
Sample plate 3
Average
Ang-Np50B-Na 5-2-5 45%
m/z
Inte
nsity/ a
.u.
1300 1320 1340
0
5000
10000
[Ang+2Na-H]+
[Ang-K]+
[Ang-Na]+
[Ang-H]+
Sample plate 1
Sample plate 2
Sample plate 3
Average
Ang-Np9B-Na 5-5-5 45%
m/z
Inte
nsity/ a
.u.
200 300 400 500 600 700 800 900
0
5000
10000
15000
20000
m/z
Inte
nsity/ a
.u.
PEG-Np18B-Na 5-7-5_35%
Sample plate 1
Sample plate 2
Sample plate 3
Average
PEG-Na+
PEG-K+
89
10
11
12
13 14
15
16
17
18
19
200 300 400 500 600 700 800 900
0
5000
10000
15000
20000
m/z
Inte
nsity/ a
.u.
PEG-Np17B-Na 5-7-5_35%
Sample plate 1
Sample plate 2
Sample plate 3
Average
PEG-Na+
PEG-K+
19
18
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16
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14
13
12
11
10
9
8
7
200 400 600 800
0
2000
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6000
PEG-Np45B-Na 5-2-5_35%
Inte
nsity/ a
.u.
m/z
Sample plate 1
Sample plate 2
Sample plate 3
Average
PEG-Na+
PEG-K+
12 13
14
15
16
17
18
19
11
10
9
8
7
NPs synthesized in citrate: 25B at 1064 nm NPs 9B at 532 nm NPs50B at 266 nm
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