Ion sources for molecular mass spectrometry are usually driven by direct current power supplies with no user control over the total charges generated. Here, we show that the output of triboelectric nanogenerators (TENGs) can quantitatively control the total ionization charges in mass spectrometry. The high output voltage of TENGs can generate single- or alternating-polarity ion pulses, and is ideal for inducing nanoelectrospray ionization (nanoESI) and plasma discharge ionization. For a given nanoESI emitter, accurately controlled ion pulses ranging from 1.0 to 5.5 nC were delivered with an onset charge of 1.0 nC. Spray pulses can be generated at a high frequency of 17 Hz (60 ms in period) and the pulse duration is adjustable on-demand between 60 ms and 5.5 s. Highly sensitive (∼0.6 zeptomole) mass spectrometry analysis using minimal sample (18 pl per pulse) was achieved with a 10 pg ml−1 cocaine sample. We also show that native protein conformation is conserved in TENG-ESI, and that patterned ion deposition on conductive and insulating surfaces is possible.
Subscribe to Journal
Get full journal access for 1 year
only $15.58 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Maher, S., Jjunju, F. P. M. & Taylor, S. Colloquium: 100 years of mass spectrometry: perspectives and future trends. Rev. Mod. Phys. 87, 113–135 (2015).
Louris, J. N. et al. Instrumentation, applications, and energy deposition in quadrupole ion-trap tandem mass-spectrometry. Anal. Chem. 59, 1677–1685 (1987).
Bohrer, B. C., Mererbloom, S. I., Koeniger, S. L., Hilderbrand, A. E. & Clemmer, D. E. Biomolecule analysis by ion mobility spectrometry. Annu. Rev. Anal. Chem. 1, 293–327 (2008).
Ruotolo, B. T., Benesch, J. L. P., Sandercock, A. M., Hyung, S. J. & Robinson, C. V. Ion mobility-mass spectrometry analysis of large protein complexes. Nat. Protoc. 3, 1139–1152 (2008).
Gross, M. L. & Rempel, D. L. Fourier transform mass spectrometry. Science 226, 261–268 (1984).
Hu, Q. Z. et al. The orbitrap: a new mass spectrometer. J. Mass Spectrom. 40, 430–443 (2005).
Contino, N. C., Pierson, E. E., Keifer, D. Z. & Jarrold, M. F. Charge detection mass spectrometry with resolved charge states. J. Am. Soc. Mass Spectrom. 24, 101–108 (2013).
Webb, I. K. et al. Mobility-resolved ion selection in uniform drift field ion mobility spectrometry/mass spectrometry: dynamic switching in structures for lossless ion manipulations. Anal. Chem. 86, 9632–9637 (2014).
Liang, X. R., Han, H. L., Xia, Y. & McLuckey, S. A. A pulsed triple ionization source for sequential ion/ion reactions in an electrodynamic ion trap. J. Am. Soc. Mass Spectrom. 18, 369–376 (2007).
Bushey, J. M., Kaplan, D. A., Danell, R. M. & Glish, G. L. Pulsed nano-electrospray ionization: characterization of temporal response and implementation with a flared inlet capillary. Instrum. Sci. Technol. 37, 257–273 (2009).
Xu, W., Charipar, N., Kirleis, M. A., Xia, Y. & Ouyang, Z. Study of discontinuous atmospheric pressure interfaces for mass spectrometry instrumentation development. Anal. Chem. 82, 6584–6592 (2010).
Schilling, M., Janasek, D. & Franzke, J. Electrospray-ionization driven by dielectric polarization. Anal. Bioanal. Chem. 391, 555–561 (2008).
Huang, G. M., Li, G. T. & Cooks, R. G. Induced nanoelectrospray ionization for matrix-tolerant and high-throughput mass spectrometry. Angew. Chem. Int. Ed. 50, 9907–9910 (2011).
Li, A., Hollerbach, A., Luo, Q. & Cooks, R. G. On-demand ambient ionization of picoliter samples using charge pulses. Angew. Chem. Int. Ed. 54, 6893–6895 (2015).
Wang, Z. L. Triboelectric nanogenerators as new energy technology for self-powered systems and as active mechanical and chemical sensors. ACS Nano 7, 9533–9557 (2013).
Wang, Z. L., Chen, J. & Lin, L. Progress in triboelectric nanogenerators as a new energy technology and self-powered sensors. Energy Environ. Sci. 8, 2250–2282 (2015).
Wang, Z. L. Triboelectric nanogenerators as new energy technology and self-powered sensors - principles, problems and perspectives. Faraday Discuss. 176, 447–458 (2014).
Tang, W. et al. Implantable self-powered low-level laser cure system for mouse embryonic osteoblasts proliferation and differentiation. ACS Nano 9, 7867–7873 (2015).
Niu, S. M., Wang, X. F., Yi, F., Zhou, Y. S. & Wang, Z. L. A universal self-charging system driven by random biomechanical energy for sustainable operation of mobile electronics. Nat. Commun. 6, 8795 (2015).
McCarty, L. S. & Whitesides, G. M. Electrostatic charging due to separation of ions at interfaces: contact electrification of ionic electrets. Angew. Chem. Int. Ed. 47, 2188–2207 (2008).
Baytekin, H. T. et al. The mosaic of surface charge in contact electrification. Science 333, 308–312 (2011).
Wang, S. et al. Molecular surface functionalization to enhance the power output of triboelectric nanogenerators. J. Mater. Chem. A 4, 3728–3734 (2016).
Zhu, G., Chen, J., Zhang, T. J., Jing, Q. S. & Wang, Z. L. Radial-arrayed rotary electrification for high performance triboelectric generator. Nat. Commun. 5, 3426 (2014).
Chen, J. et al. Harmonic-resonator-based triboelectric nanogenerator as a sustainable power source and a self-powered active vibration sensor. Adv. Mater. 25, 6094–6099 (2013).
Zi, Y. et al. Effective energy storage from a triboelectric nanogenerator. Nat. Commun. 7, 10987 (2016).
Zi, Y. et al. Standards and figure-of-merits for quantifying the performance of triboelectric nanogenerators. Nat. Commun. 6, 8376 (2015).
Wei, Z. et al. Pulsed direct current electrospray: enabling systematic analysis of small volume sample by boosting sample economy. Anal. Chem. 87, 11242–11248 (2015).
Marginean, I., Nemes, P. & Vertes, A. Astable regime in electrosprays. Phys. Rev. E 76, 026320 (2007).
Whelan, M. et al. Determination of anthelmintic drug residues in milk using ultra high performance liquid chromatography-tandem mass spectrometry with rapid polarity switching. J. Chromatogr. A 1217, 4612–4622 (2010).
Nazari, M. & Muddiman, D. C. Polarity switching mass spectrometry imaging of healthy and cancerous hen ovarian tissue sections by infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI). Analyst 141, 595–605 (2016).
Harris, G. A., Kwasnik, M. & Fernandez, F. M. Direct analysis in real time coupled to multiplexed drift tube ion mobility spectrometry for detecting toxic chemicals. Anal. Chem. 83, 1908–1915 (2011).
Allen, S. J., Schwartz, A. M. & Bush, M. F. Effects of polarity on the structures and charge states of native-like proteins and protein complexes in the gas phase. Anal. Chem. 85, 12055–12061 (2013).
Wampler, F. M., Blades, A. T. & Kebarle, P. Negative ion electrospray mass spectrometry of nucleotides: ionization from water solution with SF6 discharge suppression. J. Am. Soc. Mass Spectrom. 4, 289–295 (1993).
Monge, M. E., Harris, G. A., Dwivedi, P. & Fernandez, F. M. Mass spectrometry: recent advances in direct open air surface sampling/ionization. Chem. Rev. 113, 2269–2308 (2013).
Verbeck, G., Hoffmann, W. & Walton, B. Soft-landing preparative mass spectrometry. Analyst 137, 4393–4407 (2012).
Tyo, E. C. & Vajda, S. Catalysis by clusters with precise numbers of atoms. Nat. Nanotech. 10, 577–588 (2015).
Johnson, G. E., Colby, R., Engelhard, M., Moon, D. & Laskin, J. Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen. Nanoscale 7, 12379–12391 (2015).
Ouyang, Z. et al. Preparing protein microarrays by soft-landing of mass-selected ions. Science 301, 1351–1354 (2003).
Ju, J., Yamagata, Y. & Higuchi, T. Thin-film fabrication method for organic light-emitting diodes using electrospray deposition. Adv. Mater. 21, 4343–4347 (2009).
Bender, F., Wachter, L., Voigt, A. & Rapp, M. Deposition of high quality coatings on saw sensors using electrospray. Proc. IEEE Sensors 1, 115–119 (2003).
Li, A. et al. Using ambient ion beams to write nanostructured patterns for surface enhanced raman spectroscopy. Angew. Chem. Int. Ed. 53, 12528–12531 (2014).
This work was jointly supported by the National Science Foundation (NSF) and the NASA Astrobiology Program, under the NSF Center for Chemical Evolution, CHE-1504217. Research was also supported by the US Department of Energy, Office of Basic Energy Sciences (award DE-FG02-07ER46394) and the National Science Foundation (DMR-1505319).
The authors declare no competing financial interests.
About this article
Cite this article
Li, A., Zi, Y., Guo, H. et al. Triboelectric nanogenerators for sensitive nano-coulomb molecular mass spectrometry. Nature Nanotech 12, 481–487 (2017). https://doi.org/10.1038/nnano.2017.17
Sustainable high-voltage source based on triboelectric nanogenerator with a charge accumulation strategy
Energy & Environmental Science (2020)
Ultrasonic-assisted ultrafast fabrication of polymer nanowires for high performance triboelectric nanogenerators
Nano Energy (2020)
ACS Applied Materials & Interfaces (2020)
Angewandte Chemie (2020)
Enhanced mechanical energy harvesting capability in sodium bismuth titanate based lead-free piezoelectric
Journal of Alloys and Compounds (2020)